JP5102966B2 - Metalworking oil composition - Google Patents

Description

  The present invention relates to metalworking oil compositions.

  In cutting and grinding, productivity improvement 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 this purpose, oils for cutting and grinding are 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. 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.

  Cutting and grinding fluids effective for improving the processing efficiency are not preferable from another aspect, and a typical problem is the influence on the environment. Regardless of water-insolubility and water-solubility, oils gradually deteriorate during use and eventually become unusable. For example, in the case of a water-soluble oil agent, the stability of the liquid is reduced due to the generation of microorganisms, resulting in separation of components, or the sanitary environment is significantly reduced, making its use impossible. Further, in the case of a water-insoluble oil agent, an acidic component generated by the progress of oxidation corrodes the metal material or causes a significant change in viscosity, making it impossible to use. Further, the oil agent adheres to chips and is consumed and becomes waste.

  In such a case, the deteriorated oil is discarded and a new oil is used. At this time, the oil discharged as waste requires various treatments so as not to affect the environment. For example, cutting and grinding fluids that have been developed with a priority on improving work efficiency often use chlorinated compounds that may generate toxic dioxins during incineration. Processing is required. For this reason, cutting and grinding fluids that do not contain chlorinated compounds have also been developed, but even with such cutting and grinding fluids that do not contain such harmful components, there is a problem of the environmental impact associated with the massive discharge of waste. is there. Further, in the case of water-soluble oils, there is a possibility of polluting the environmental water area, so it is necessary to perform advanced treatment at high cost.

  Thus, as an example where it is difficult to achieve both improvement in processing efficiency and reduction in environmental load, there is a manufacturing field of non-ferrous metal parts used as automobile parts and household appliance parts. More specifically, when processing non-ferrous metal parts such as aluminum or aluminum alloys, conventionally, a water-soluble oil agent is generally used, but the waste liquid after processing the non-ferrous metal is a metal. Is often dissolved, and there is a problem that a large amount of cost is required for waste liquid treatment. In addition, when using a water-soluble oil agent, if a processing solution having an optimum pH is not used, rot and corrosion of the surface of the component occur. Therefore, strict and frequent management is required for its use.

  Therefore, in the field of non-ferrous metal processing, in order to solve the above-mentioned problems, application of dry processing and water-insoluble processing oil is being studied.

  On the other hand, as a new processing method, development of a cutting / grinding method for supplying a very small amount of oil has been promoted. In this method, cutting / grinding is performed while supplying an extremely small amount of oil, which is about 1 / 100,000 to 1 / 1000,000, together with a compressed fluid (for example, compressed air) to the work piece compared to the amount of oil used in normal cutting / grinding. Is what you do. In this system, a cooling effect by compressed air can be obtained, and the amount of waste can be reduced because a very small amount of oil is used. Therefore, the influence on the environment due to a large amount of waste can be improved. Therefore, this method is expected not only as a nonferrous metal processing method but also as a ferrous metal processing method.

  In the case of a very small amount of oil supply system, it is desirable that a good surface workpiece can be obtained even if the amount of oil supplied is extremely small, and that the wear of tools, etc. is low, and that cutting and grinding can be performed efficiently. Therefore, higher performance is required for cutting and grinding fluids. Moreover, it is desirable that it is an oil agent excellent in biodegradability from the point of a waste disposal or a work environment.

  In addition, in the case of a very small amount of oil supply system, it is very important to generate good oil mist. If the oil mist is in a bad state, piping clogging occurs and the amount of oil reaching the machining point becomes insufficient, and the machining efficiency and tool life are likely to be reduced. On the other hand, if the oil is easily misted excessively, the discharged oil mist will scatter and contaminate the work environment. Also in this case, since the oil amount is lost due to the scattering of the oil mist, the amount of oil reaching the processing point becomes insufficient, and the processing efficiency and the tool life are likely to decrease.

  In addition, in the trace amount oil supply system, the oil is supplied after being made into an oil mist, so if an unstable oil is used, it will stick to the inside of the machine tool, workpiece, tool, mist collector, etc. This causes trouble in handling and reduces work efficiency. Therefore, it is desirable that the oil agent is not sticky in the development of the oil agent used in the ultra-trace oil agent supply method.

In view of such a situation, the present inventors have proposed a metalworking oil composition of a trace amount oil agent supply system containing both ester oil and hydrocarbon oil having a specific kinematic viscosity (patent) Reference 1).
: JP-A-2005-290163

  The present invention is further excellent in characteristics as a water-insoluble oil for non-ferrous metal processing and as a cutting / grinding oil in a very small amount of oil supply system, and improves machining efficiency and further extends tool life. It aims at providing the metal processing oil composition of the trace amount oil supply system which can be achieved.

The present invention comprises an ester oil in an amount of 20 to 95% by mass based on the entire composition , a Fischer-Tropsch (FT) synthesis step, a hydrocracking step of a wax-containing component, and a hydrorefining treatment step of components obtained from these steps. A kerosene fraction produced by a production process having at least one process selected from: a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , and an n-paraffin content of 10 to 90% by mass . , to provide a metal working oil composition characterized in that the aromatic content of 0-3% by volume, naphthene contains 5-70 wt% of the total amount of the composition of the hydrocarbon oil is 0 to 20 volume% .

  Excellent characteristics as a water-insoluble oil for non-ferrous metal processing and as an oil for cutting and grinding with a very small amount of oil supply system, enabling improved machining efficiency and longer tool life. In particular, it is possible to improve the workability, particularly the mist formation characteristics, in the metal processing of the trace amount oil supply system.

The metalworking oil of this invention contains (A) ester oil. First, the ester oil will be explained.
This ester oil may be a natural product (usually contained in natural fats and oils such as animals and plants) or a synthetic product. In the present invention, a synthetic ester is preferable from the viewpoint of the stability of the resulting lubricating oil and the uniformity of the ester component. Moreover, it is preferable that it is a natural ester from the point of influence with respect to an environment.

  (A) The alcohol constituting the ester oil may be a monohydric alcohol or a polyhydric alcohol, and the acid constituting the ester oil may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, and saturated. Or may be unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecane Decanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol, linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as linear or branched tetracosanol, and mixtures thereof.

  As the polyhydric alcohol, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof That.

  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, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, and a mixture thereof are most preferable because higher thermal and oxidation stability can be obtained.

  (A) The alcohol constituting the ester oil may be either a monohydric alcohol or a polyhydric alcohol as described above, but it has a low pour point, as well as a better lubricity. Polyhydric alcohols are preferred from the standpoints of being easier to obtain and improving handling in winter and cold regions. In addition, when polyhydric alcohol ester oil is used, in cutting and grinding, the finished surface accuracy of the workpiece is improved, and the effect of preventing wear of the tool edge is further increased.

  Of the acids constituting the ester oil (A), 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 saturated. However, it may be 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, in particular, saturated fatty acids having 3 to 20 carbon atoms, unsaturated fatty acids having 3 to 22 carbon atoms, and mixtures thereof are preferable, and saturated fatty acids having 4 to 18 carbon atoms. The unsaturated fatty acid having 4 to 18 carbon atoms and a mixture thereof are more preferable, the unsaturated fatty acid having 4 to 18 carbon atoms is more preferable, and the saturated fatty acid having 4 to 18 carbon atoms is more preferable from the viewpoint of stickiness prevention.

  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.

(A) The acid constituting the ester oil may be a monobasic acid or a polybasic acid as described above, but when a monobasic acid is used, the viscosity index is improved and the anti-sticking property is improved. It is preferable because an ester that contributes to the above is easily obtained.

(A) The combination of the alcohol and the acid forming the ester is arbitrary and is not particularly limited. Examples of the ester oil that can be used in the present invention include the following esters.

(I) ester of monohydric alcohol and monobasic acid (ii) ester of polyhydric alcohol and monobasic acid (iii) ester of monohydric alcohol and polybasic acid (iv) polyhydric alcohol and polybasic acid (V) Monohydric alcohol, mixed ester of polyhydric alcohol and polybasic acid (vi) Mixed ester of polyhydric alcohol and monobasic acid, polybasic acid (vii) Monohydric alcohol A mixed ester of a mixture of a polyhydric alcohol and a monobasic acid or polybasic acid

  Among these, it is easier to obtain a product with higher lubricity, a lower pour point, easier handling in winter and cold regions, and a higher viscosity index (ii). It is preferably an ester of a polyhydric alcohol and a monobasic acid.

  In addition, as the natural product-derived ester used in the present invention, palm oil, palm kernel oil, rapeseed oil, soybean oil, sunflower oil, and oleic acid in fatty acids constituting glycerides by breeding or genetic recombination operations, etc. Examples include natural oils and fats such as vegetable oils such as high oleic rapeseed oil and high oleic sunflower oil, and animal oils such as lard.

  Among these natural product-derived esters, high-oleic natural fats and oils with an increased content of oleic acid are preferred from the viewpoint of the stability of the lubricating oil. Triesters of fatty acids and glycerin (hereinafter simply referred to as “triesters”) And 40 to 98% by mass of the fatty acid is particularly preferred. By using such triesters, both lubricity and thermal / oxidative stability can be achieved at a high level in a well-balanced manner. Further, the content of oleic acid in the fatty acid constituting the triester is preferably 50% by mass or more, more preferably, from the viewpoint that both lubricity and thermal / oxidative stability can be achieved at a high level in a balanced manner. It is 60% by mass or more, more preferably 70% by mass or more, and from the same point, it is preferably 95% by mass or less, more preferably 90% by mass or less.

  In addition, the ratio of oleic acid in the fatty acid (hereinafter referred to as “constituent fatty acid”) constituting the triester and the ratio of linoleic acid and the like described below are determined according to the standard oil analysis method 2.4. It is measured in accordance with Item 2 “Fatty Acid Composition”.

  In addition, fatty acids other than oleic acid among the constituent fatty acids of the triester are not particularly limited as long as they do not impair lubricity and thermal / oxidative stability, but are preferably fatty acids having 6 to 24 carbon atoms. The fatty acid having 6 to 24 carbon atoms may be a saturated fatty acid or an unsaturated fatty acid having 1 to 5 unsaturated bonds. In addition, the fatty acid may be linear or branched. Furthermore, you may have 1-3 hydroxyl groups (-OH) other than a carboxyl group (-COOH) in a molecule | numerator. Specific examples of such fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, lauroleic acid, myristoleic acid, palmitolein. Examples include acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, ricanoic acid, arachidonic acid, and carbadoic acid. Among these fatty acids, linoleic acid is preferable in terms of both lubricity and thermal / oxidative stability, and is preferably 1 to 60% by mass (more preferably 2 to 50% by mass, still more preferably) of the fatty acid constituting the triester. 4 to 40% by mass) is more preferably linoleic acid.

  Furthermore, in said triester, 0.1-30 mass% (more preferably 0.5-20 mass% in a constituent fatty acid) in the point of coexistence of lubricity and heat | fever and oxidation stability, More preferably 1 to 10% by mass) is preferably a fatty acid having 6 to 16 carbon atoms. When the proportion of the fatty acid having 6 to 16 carbon atoms is less than 0.1% by mass, the heat / oxidation stability tends to decrease, and when it exceeds 30% by mass, the lubricity tends to decrease.

  The total unsaturation degree of the triester is preferably 0.3 or less, and more preferably 0.2 or less. When the total degree of unsaturation of the triester is greater than 0.3, the thermal / oxidative stability of the lubricating oil of the present invention tends to deteriorate. The total degree of unsaturation referred to in the present invention is measured by the same apparatus / operation method in accordance with JIS K 1557-1970 “Polyurethane Polyether Test Method” except that a triester is used instead of the polyether for polyurethane. The total degree of unsaturation.

  As the triester according to the present invention, as long as the ratio of oleic acid in the constituent fatty acid satisfies the above conditions, one obtained by synthesis may be used, or a vegetable oil containing the triester, etc. Although natural oil may be used, it is preferable to use natural oil such as vegetable oil from the viewpoint of safety to the human body. As such vegetable oil, rapeseed oil, sunflower oil, soybean oil, corn oil and canola oil are preferred, and sunflower oil, rapeseed oil and soybean oil are particularly preferred.

  Here, many of the natural vegetable oils have a total unsaturation level exceeding 0.3, but the total unsaturation level can be reduced by treatment such as hydrogenation in the refining process. In addition, vegetable oils having a low total unsaturation can be easily produced by gene recombination techniques. For example, high oleic acid soybean oil, high oleic sunflower oil, high oleic acid canola oil, etc. having a total unsaturation of 0.3 or less and oleic acid being 70% by mass or more, An oleic rapeseed oil etc. can be illustrated.

  In the present invention, the ester obtained when a polyhydric alcohol is used as the alcohol component may be a complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified. A partial ester may be used. The organic acid ester obtained when a polybasic acid is used as the acid component may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, or a part of the carboxyl groups is not esterified and carboxylated. It may be a partial ester remaining as a group.

The iodine value of the (A) ester oil is preferably 0 to 80, more preferably 0 to 60, still more preferably 0 to 40, still more preferably 0 to 20, and most preferably 0 to 10. Further, bromine number of the ester according to the present invention is preferably 0~50gBr ₂ / 100g, more preferably 0~30gBr ₂ / 100g, more preferably 0~20gBr ₂ / 100g, most preferably 0~10gBr ₂ / 100g It is. If the iodine value and bromine value of the ester are within the above ranges, the resulting lubricating oil tends to be more anti-sticky. The iodine value referred to here is a value measured by the indicator titration method of JIS K 0070 “Measurement method of acid value, saponification value, ester value, iodine value, hydroxyl value and non-saponification value of chemical products”. Say. The bromine number is a value measured by JIS K 2605 “Chemical product—Bromine number test method—Electro titration method”.

  Moreover, in order to give further better lubricating performance to the metalworking oil composition of the present invention, (A) the ester oil has a hydroxyl value of 0.01 to 300 mgKOH / g, and a ken value of 100 to 500 mgKOH / g. It is preferable that In the present invention, the upper limit of the hydroxyl value of the ester for obtaining higher lubricity is more preferably 200 mgKOH / g, most preferably 150 mgKOH / g, while the lower limit is more preferably 0.1 mgKOH. / G, more preferably 0.5 mgKOH / g, even more preferably 1 mgKOH / g, even more preferably 3 mgKOH / g, and most preferably 5 mgKOH / g. Further, the upper limit of the saponification value of (A) ester oil is more preferably 400 mgKOH / g, while the lower limit thereof is more preferably 200 mgKOH / g. The hydroxyl value referred to here is a value measured by an indicator titration method according to JIS K 0070 “Method for measuring acid value, saponification value, ester value, iodine value, hydroxyl value and non-saponification value of a chemical product”. Say. The saponification value is a value measured by an indicator titration method of JIS K 2503 “Aeronautical Lubricating Oil Test Method”.

No particular limitation is imposed on the kinematic viscosity of (A) ester oil, the kinematic viscosity at 40 ° C., preferably not more than 300 mm ² / s, more preferably not more than 200 mm ² / s, more preferably 100 mm ² / s or less, particularly preferably 75 mm ² / s or less. The kinematic viscosity of the ester is preferably 1 mm ² / s or more, more preferably 3 mm ² / s or more, and further preferably 5 mm ² / s or more.

  (A) Although there is no restriction | limiting in particular in the pour point and viscosity index of ester oil, It is preferable that it is -10 degrees C or less, More preferably, it is -20 degrees C or less. The viscosity index is desirably 100 or more and 200 or less.

The content of (A) an ester oil in metalworking oil composition of the present invention is 9 5 mass% or less, good Mashiku 90 mass% or less, more preferably 80 wt% or less, more preferably it is 70 wt% or less . When the content exceeds 95% by mass, the welding is increased, the machining resistance is increased, and the machining efficiency and the tool life tend to be lowered. Further, the content of (A) ester oil, the total amount of the composition, 2 0% by mass or more, good Mashiku 30 mass% or more, and more preferably at least 40 wt%. When the content is less than 10 masses, the welding is increased, the machining resistance is increased, and the machining efficiency and the tool life tend to be reduced. In addition, when used for cutting and processing of a trace amount oil supply system, biodegradability tends to be reduced.

Below, the (B) hydrocarbon oil of this invention used together with the said ester oil is explained in full detail.
Hydrocarbon oil The density at 15 ° C. of the present invention is 0.7 to 0.8 g / cm ³ , the n-paraffin content is 10 to 90%, the aromatic content is 0 to 3%, and the naphthene content is 0 to 20%. (B) Properties of the hydrocarbon oil are as follows.
The density (15 ° C., JISK 2249) of the hydrocarbon oil of the present invention is 0.70 to 0.80, preferably 0.72 to 0.79, and more preferably 0.73 to 0.785. Lower density results in lower flash point.
Although 40 degreeC kinematic viscosity (mm < ² > / s, JISK2283) is not specifically limited, Preferably it is 0.5-9.0, More preferably, it is 1.0-5.5, More preferably, it is 1.2-4.0. It is. The lower the kinematic viscosity, the lower the flash point.
The flash point (° C.) is measured by a tag-sealed type or pen schema tenth-type flash point test method according to JIS K2265, and is not particularly limited, but is preferably 50-200, more preferably 55-150, More preferably, it is 58-140. A lower flash point is undesirable because safety is compromised.

Distillation properties (° C.) were determined by Engler distillation (JIS K2254) and are as follows.
The initial boiling point (° C.) is 140 to 280, preferably 150 or more and 275 or less, more preferably 160 to 270, and further preferably 165 to 285.
The 10% distillation point (° C.) is not particularly limited, but is preferably 150 or more and 290 or less, more preferably 160 to 285, still more preferably 170 to 280, and particularly preferably 180 to 275.
The 50% distillation point (° C.) is not particularly limited, but is preferably 170 or more and 320 or less, more preferably 180 to 310, still more preferably 190 to 300, and particularly preferably 195 to 290.
The 90% distillation point (° C.) is not particularly limited, but is preferably 180 or more and 390 or less, more preferably 190 to 370, still more preferably 200 to 340, and particularly preferably 210 to 330.
The end point (° C.) is 190 to 400, preferably 200 or more and 380 or less, more preferably 210 to 350, and still more preferably 220 to 340.
T ₉₀ -T ₁₀ (℃) is not particularly limited, but is preferably 15 or more, 160 or less, more preferably 20 to 150, more preferably 30 to 140, particularly preferably from 35 to 135.
Although EP-IBP (degreeC) is not specifically limited, Preferably it is 35 or more and 200 or less, More preferably, it is 40-190, More preferably, it is 50-180, Most preferably, it is 60-170.

The smoke point (mm, JISK 2537) is not particularly limited, but is preferably 30 or more, more preferably 35 or more, still more preferably 40 or more and 60 or less, and particularly preferably 50 or more and 110 or less.
The aniline point (° C., JISK2256) is not particularly limited, but is preferably 65 or more, more preferably 70 or more, and further preferably 75 or more. An aniline point lower than this is not preferable because the processing performance deteriorates.
Sulfur content (mass ppm, JIS K2541) is 0-30. Preferably it is 10 or less, More preferably, it is 5 or less, More preferably, it is 1 or less. If it is larger than this, there is an effect of odor, which is not preferable.
The cetane index (JIS K2280) is 55 or more, preferably 60 or more, more preferably 65 or more, and still more preferably 70 or more. If it is lower than this, the processing performance deteriorates, which is not preferable.

The composition is as follows.
The saturation (volume%) is 90 or more. Preferably it is 97 or more, More preferably, it is 98 or more, More preferably, it is 99 or more, Most preferably, it is 100 or more. If it is less than this, the processing performance deteriorates, which is not preferable.
The unsaturated content (volume%) is not particularly limited, but is preferably 5 or less, more preferably 3 or less, and still more preferably 1 or less.
The aromatic content (volume%) is 10 or less. It is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less, and particularly preferably one that does not substantially contain an aromatic component. Aromatic components are not preferred because they can worsen odor and adversely affect the human body.
In addition, the saturated content, the unsaturated content, and the aromatic content referred to here are measured in accordance with the Petroleum Institute method JPI-5S-49-97 “hydrocarbon type test method—high performance liquid chromatograph method”. It means the volume percentage (volume%) (based on the total amount of diluent oil) of the aromatic content measured according to (published by the Japan Petroleum Institute).
The n-paraffin content (% by mass) is 10-90, preferably 20-80, and more preferably 30-70. When the amount is less than this range, the processability is inferior, and when it is more, the compatibility with the ester oil (A) is inferior.
In addition, n-paraffin content here means the value (dilution oil whole quantity reference | standard) measured using GC-FID. In the present invention, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, the column length is 30 m, and the carrier gas flow rate is 1.0 mL / Identification using a standard sample containing n-paraffin under the conditions of min, split ratio 1:79, sample injection temperature 360 ° C., column heating condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C. The quantified n-paraffin content (based on the total amount of diluent oil) is shown, but the measurement conditions are not limited as long as equivalent results are obtained.
The upper limit of the naphthene content (volume%) of the hydrocarbon oil of the present invention is 20% or less, preferably 10% or less, more preferably 5% or less. If the naphthene content is high, an odor is emitted, which leads to deterioration of the working environment and also causes skin irritation.
Here, the paraffin content and naphthene content are measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”. It means volume percentage (volume%) (based on the total amount of saturation).

As mentioned above, although the hydrocarbon oil of this invention has been demonstrated, the following 1st aspect is mentioned as a more concrete preferable aspect.
That is, (B1) a base oil having an initial boiling point of 200 ° C. or lower and a flash point of 50 ° C. or higher is preferable. The properties of the base oil (B1) are as follows.
The density (15 ° C.) is not particularly limited, but is preferably 0.70 to 0.80, more preferably 0.72 to 0.79, and even more preferably 0.74 to 0.76. Although (mm < ² > / s) is not specifically limited, Preferably it is 0.5-3.0, More preferably, it is 1.0-2.5, More preferably, it is 1.2-2.0. By setting it within this range, a highly viscous lubricating oil can be used.
The flash point (TC) (° C.) is 50 or more, preferably 50 to 100, more preferably 55 to 80, and still more preferably 55 to 65.

Distillation properties (° C.) were determined by Engler distillation (JIS K2254) and are as follows.
Although an initial boiling point (degreeC) is 200 degrees C or less, Preferably it is 150 or more and 200 or less, More preferably, it is 160-180, More preferably, it is 165-175.
The 10% distillation point (° C.) is not particularly limited, but is preferably 160 or more and 210 or less, more preferably 170 to 200, and still more preferably 180 to 190.
The 50% distillation point (° C.) is not particularly limited, but is preferably 170 or more and 230 or less, more preferably 180 to 220, and still more preferably 190 to 210.
The 90% distillation point (° C.) is not particularly limited, but is preferably 190 or more and 250 or less, more preferably 200 to 240, and still more preferably 210 to 230.
The end point (° C.) is 190 to 400, preferably 210 or more and 270 or less, more preferably 220 to 260, and still more preferably 230 to 250.
T ₉₀ -T ₁₀ (℃) is not particularly limited, but is preferably 15 or more, 70 or less, more preferably 20 to 60, more preferably from 30 to 50.
EP-IBP (° C.) is not particularly limited, but is preferably 35 or more and 110 or less, more preferably 40 to 100, and still more preferably 50 to 90.

Although an aniline point (degreeC) is not specifically limited, Preferably it is 65 or more, More preferably, it is 70-90, More preferably, it is 75-85. Within this range, the machining performance is improved.
The cetane index (JIS K2280) is 55 or more, preferably 60 to 199, more preferably 65 to 90, and still more preferably 70 to 80. The machining performance is improved within this range.

The composition is as follows.
The n-paraffin content (% by mass) is 10-90, preferably 20-80, and more preferably 30-70. When the amount is less than this range, the processability is inferior, and when it is more, the compatibility with the ester oil (A) is inferior.

The base oil (B) of the present invention is more preferably (B2): a base oil having an initial boiling point of 200 ° C. or higher, a flash point of 70 ° C. or higher, and a cetane index of 60 or higher.
The properties of the diluted oil (B2) are as follows.
The density (15 ° C.) is not particularly limited, but is preferably 0.70 to 0.80, more preferably 0.72 to 0.79, still more preferably 0.74 to 0.785, and particularly preferably 0.00. 76-0.785. By setting it within this range, a high flash point can be obtained.
Although 40 degreeC kinematic viscosity (mm < ² > / s) is not specifically limited, Preferably it is 2.0-9.0, More preferably, it is 2.5-5.5, More preferably, it is 3.0-5.0. . By setting it within this range, a high flash point can be obtained.
The flash point (TC) (° C.) is 50 or more, preferably 70 to 200, more preferably 80 to 150, still more preferably 100 to 140, and particularly preferably 120 to 140. By making it within this range, safety can be improved.

Distillation properties (° C.) were determined by Engler distillation (JIS K2254) and are as follows.
Although an initial boiling point (degreeC) is 200 degrees C or less, Preferably it is 210-270, More preferably, it is 2200-260.
The 10% distillation point (° C.) is not particularly limited, but is preferably 210 or more and 290 or less, more preferably 220 to 285, still more preferably 230 to 280, and particularly preferably 240 to 275.
The 50% distillation point (° C.) is not particularly limited, but is preferably 230 or more and 320 or less, more preferably 240 to 310, still more preferably 250 to 300, and particularly preferably 260 to 290.
The 90% distillation point (° C.) is not particularly limited, but is preferably 250 or more and 390 or less, more preferably 260 to 370, still more preferably 270 to 340, and particularly preferably 280 to 330.
The end point (° C.) is 190 to 400, preferably 270 or more and 400 or less, more preferably 280 to 380, and still more preferably 290 to 350.
T ₉₀ -T ₁₀ (℃) is not particularly limited, but is preferably 15 or more, 70 or less, more preferably 20 to 60, more preferably from 30 to 50.
EP-IBP (° C.) is not particularly limited, but is preferably 35 or more and 110 or less, more preferably 40 to 100, and still more preferably 50 to 90.

Although an aniline point (degreeC) is not specifically limited, Preferably it is 65 or more, More preferably, it is 75-110, More preferably, it is 85-105.
The cetane index (JIS K2280) is 55 or more, preferably 60 to 110, more preferably 65 to 100, and still more preferably 70 to 95.

The composition is as follows.
The n-paraffin content (% by mass) is 10-90, preferably 20-80, and more preferably 30-70. When the amount is less than this range, the processability is inferior, and when it is more, the compatibility with the ester oil (A) is inferior.

The production method of the hydrocarbon oil of the present invention is at least one step selected from a Fischer-Tropsch (FT) synthesis step, a hydrocracking step of a wax-containing component, and a hydrorefining treatment step of components obtained from these steps. Ru Ah in kerosene and gas oil fraction produced by the production process with.
The FT synthesis process is a process in which a Fischer-Tropsch (FT) reaction is applied to a mixed gas containing hydrogen and carbon monoxide as main components (sometimes referred to as synthesis gas). Gas, naphtha, kerosene, light oil A liquid fraction corresponding to the boiling point range, paraffin wax (FT wax) and the like are obtained.
The hydrocracking process of the wax-containing component is a process of hydrocracking (which may include an isomerization reaction) a wax-containing component such as slack wax by-produced in the FT wax or lubricating oil dewaxing process. Yes, a liquid fraction, lubricating oil fraction, etc. corresponding to the boiling range of gas, naphtha, kerosene, and light oil can be obtained.
The hydrorefining step is a step of hydrorefining (which may include a hydrocracking / isomerization reaction) a component obtained from either or both of the above two steps.
In the present invention, the kerosene fraction obtained from each of the above steps may be used singly or as a mixture of two or more, and the kerosene fraction obtained from different above steps may be used as a mixture of two or more. May be.
Here, the kerosene oil fraction means a fraction having a boiling range in the range of 140 to 400 ° C., preferably 150 to 360 ° C. at normal pressure. For example, the kerosene fraction generally has a boiling point of 140 -300 degreeC, Preferably it exists in the range of 150-260 degreeC, and the light oil fraction has a boiling point in the range of 150-400 degreeC, Preferably it is in the range of 180-360 degreeC.

Below, each process of FT synthesis | combination, hydrorefining, and hydrocracking is demonstrated.
(FT synthesis process)
<Raw gas>
The mixed gas used as a raw material is a mixed gas mainly composed of hydrogen and carbon monoxide, and a substance containing carbon is oxidized using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and further required. Accordingly, it is obtained by adjusting to a predetermined hydrogen and carbon monoxide concentration by a shift reaction using water. Substances containing carbon include natural gas, petroleum liquefied gas, methane gas, etc., gas components consisting of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste such as building materials and garbage, sludge, In addition, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc. that are difficult to process by ordinary methods to high temperatures is common, but mixed gas mainly composed of hydrogen and carbon monoxide As long as is obtained, the present invention does not limit the raw materials.

<Catalyst type>
A Fischer-Tropsch reaction requires a metal catalyst. As the metal catalyst, a Group 8 metal, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, or the like, more preferably a Group 8 metal of the fourth period is used as an active catalyst component. Moreover, the metal group which mixed these metals in an appropriate amount can also be used. These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina. Further, by using these catalysts in combination with a second metal in addition to the above active metal, the catalyst performance can be improved. Examples of the second metal include alkali metal and alkaline earth metal, specifically sodium, lithium, magnesium, etc., as well as zirconium, hafnium, titanium, and the like. It is used appropriately according to the purpose, such as an increase in chain growth probability (α) as an index.

<Raw material mixed gas composition>
The Fischer-Tropsch reaction is a synthesis method for producing a liquid fraction and paraffin wax using a mixed gas as a raw material. In order to efficiently perform this synthesis method, it is generally preferable to control the ratio of hydrogen to carbon monoxide in the mixed gas. The molar mixing ratio of hydrogen and carbon monoxide is preferably 1.2: 1 or more, more preferably 1.5: 1, and even more preferably 1.8: 1 or more. This ratio is preferably 3: 1 or less, more preferably 2.6: 1 or less, and even more preferably 2.2: 1 or less.

<Reaction temperature>
When performing the Fischer-Tropsch reaction using the catalyst, the reaction temperature is preferably 180 ° C. or higher and 320 ° C. or lower, and more preferably 200 ° C. or higher and 300 ° C. or lower. When the reaction temperature is less than 180 ° C., carbon monoxide hardly reacts and the hydrocarbon yield tends to be low. On the other hand, when the reaction temperature exceeds 320 ° C., the amount of gas such as methane increases, and the production efficiency of the liquid fraction and paraffin wax decreases.

<Liquid space velocity>
No particular restriction on the gas hourly space velocity relative to the catalyst, but preferably 500h ^-1 or more 4000h ^-1 or less, 1000h ^-1 or more 3000h ^-1 or less is more preferable. If the gas space velocity is less than 500, the productivity of the liquid fuel tends to decrease. If the gas space velocity exceeds 4000 h ⁻¹ , the reaction temperature has to be increased and gas generation increases, resulting in a decrease in the yield of the target product. End up.

<Reaction pressure>
The reaction pressure (partial pressure of synthesis gas composed of carbon monoxide and hydrogen) is not particularly limited, but is preferably 0.5 MPa or more and 7 MPa or less, and more preferably 2 MPa or more and 4 MPa or less. If the reaction pressure is less than 0.5 MPa, the yield of the liquid fraction tends to decrease, and if it exceeds 7 MPa, the amount of capital investment tends to increase, which is uneconomical.

(Hydrorefining process, hydrocracking process)
The component obtained by the FT synthesis step and / or the wax-containing component is hydrorefined or hydrocracked by any method. Hydrorefining and hydrocracking may be selected in accordance with the purpose, and selection of only one or a combination of both methods is not limited in any way as long as the diluted oil of the present invention can be produced.

(Hydro-refining process)
This step is a step of hydrorefining mainly the component obtained by the FT synthesis step and / or the component obtained by the hydrocracking step of the wax-containing component described later. The reaction in this step may include a hydrogenolysis / isomerization reaction.
<Catalyst type>
A catalyst used for hydrorefining is generally a catalyst in which a hydrogenation active metal is supported on a porous carrier, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained.
Examples of the porous carrier include inorganic oxides such as alumina. Specific examples of the inorganic oxide include alumina, titania, zirconia, boria, silica, and zeolite.
Zeolite is a crystalline aluminosilicate, and includes faujasite, pentasil, mordenite, etc., preferably faujasite, beta, mordenite, particularly preferably Y type and beta type. The Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 8 metals of the Periodic Table. Preferably, it is at least one selected from Ru, Rd, Ir, Pd, and Pt, and more preferably Pd or / and Pt. The active metal may be a combination of these metals. For example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru , Ir-Pd-Rh, Ir-Rh-Ru, and the like. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
Further, as the active metal B type, it contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably contains two or more metals selected from Groups 6A and 8 What you are doing can also be used. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. When a metal sulfide catalyst made of these metals is used, it is necessary to include a preliminary sulfidation step.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

<Reaction temperature>
The reaction temperature when hydrorefining using the catalyst composed of the active metal A type is preferably 180 ° C. or higher and 400 ° C. or lower, more preferably 200 ° C. or higher and 370 ° C. or lower, more preferably 250 ° C. or higher. It is further preferably 350 ° C. or lower, and more preferably 280 ° C. or higher and 350 ° C. or lower. If the reaction temperature in hydrorefining exceeds 370 ° C., side reactions that decompose into naphtha fractions increase, and the yield of middle fractions is extremely undesirably reduced. On the other hand, when the reaction temperature is lower than 170 ° C., the alcohol component cannot be completely removed and is not preferable.
The reaction temperature when hydrotreating using a catalyst composed of the active metal B type is preferably 170 ° C. or higher and 320 ° C. or lower, more preferably 175 ° C. or higher and 300 ° C. or lower, and 180 ° C. or higher. It is still more preferable that it is 280 degrees C or less. If the reaction temperature in the hydrorefining exceeds 320 ° C., side reactions that decompose into naphtha fractions increase, and the yield of middle fractions is extremely undesirably reduced. On the other hand, when the reaction temperature is lower than 170 ° C., the alcohol component cannot be completely removed and is not preferable.

<Hydrogen pressure>
The hydrogen pressure when hydrotreating using a catalyst composed of the active metal A type is preferably 0.5 MPa or more and 12 MPa or less, and more preferably 1.0 MPa or more and 5.0 MPa or less. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen pressure when hydrorefining using the catalyst composed of the active metal B type is preferably 2 MPa or more and 10 MPa or less, more preferably 2.5 MPa or more and 8 MPa or less, and 3 MPa or more and 7 MPa or less. Even more preferably. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

<LHSV>
The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more 10.0H ^-1 or less, 0.3h ^-1 or 3 More preferably, it is 5 h ⁻¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or 1. more preferably 5h ^-1 or less, and still more preferably at 0.3h ^-1 or 1.2 h ^-1 or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

<Hydrogen / oil ratio>
The hydrogen / oil ratio when hydrorefining using the catalyst composed of the active metal A type is preferably 50 NL / L or more and 1000 NL / L or less, and preferably 70 NL / L or more and 800 NL / L or less. More preferred. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio when hydrorefining using the catalyst composed of the active metal B type is preferably 100 NL / L or more and 800 NL / L or less, and preferably 120 NL / L or more and 600 NL / L or less. More preferably, it is 150 NL / L or more and 500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

(Hydrolysis process)
This step is a step of hydrocracking the wax-containing component, preferably the FT wax. The reaction in this step may include an isomerization reaction.
<Catalyst type>
The catalyst used for hydrocracking is generally one in which a hydrogenation active metal is supported on a carrier having a solid acid property, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained. Absent.
Supports having a solid acid property include amorphous and crystalline zeolites. Specific examples include amorphous silica-alumina, silica-magnesia, silica-zirconia, silica-titania and zeolite faujasite type, beta type, MFI type, and mordenite type. Preferred are faujasite type, beta type, MFI type, and mordenite type zeolite, and more preferred are Y type and beta type. The Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal C type and active metal D type) are preferably used.
The active metal C type is mainly at least one metal selected from Group 6A and Group 8 metals of the Periodic Table. Preferably, it is at least one metal selected from Ni, Co, Mo, Pt, Pd, and W. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
The active metal D type may be a combination of these metals, such as Pt—Pd, Co—Mo, Ni—Mo, Ni—W, and Ni—Co—Mo.
Moreover, when using the catalyst which consists of these metals, it is preferable to use after pre-sulfiding.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

<Reaction temperature>
The reaction temperature when performing hydrocracking using a catalyst composed of the active metal C type and the active metal D type is preferably 200 ° C. or higher and 450 ° C. or lower, more preferably 250 ° C. or higher and 430 ° C. or lower. It is more preferably 300 ° C. or higher and 400 ° C. or lower. When the reaction temperature in hydrocracking exceeds 370 ° C., side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction is extremely reduced, which is not preferable. On the other hand, when the temperature is lower than 200 ° C., the activity of the catalyst is remarkably lowered, which is not preferable.

<Hydrogen pressure>
The hydrogen pressure when hydrocracking using a catalyst comprising the above active metal C type and active metal D type is preferably 1 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 16 MPa or less, and 6 MPa or more. Even more preferably, it is 13 MPa or less. The higher the hydrogen pressure is, the more hydrogenation reaction is promoted. However, the decomposition reaction rather slows down and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. For this reason, there is generally an economical optimum for the reaction temperature.

<LHSV>
The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal type C (LHSV) is preferably at 0.1 h ^-1 or more ^{10h -1} or less, 0.3h ^-1 or 3. More preferably, it is 5h- ¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal type D (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or 1. more preferably 7h ^-1 or less, and still more preferably at 0.3h ^-1 or more 1.5Hh ^-1 or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

<Hydrogen / oil ratio>
The hydrogen / oil ratio when hydrocracking using a catalyst composed of the above active metal C type is preferably 50 NL / L or more and 1000 NL / L or less, and preferably 70 NL / L or more and 800 NL / L or less. More preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio when hydrocracking using the catalyst composed of the active metal D type is preferably 150 NL / L or more and 2000 NL / L or less, and preferably 300 NL / L or more and 1700 NL / L or less. More preferably, it is still more preferably 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

<Device>
The apparatus for hydrotreating may be of any configuration, the reaction towers may be used alone or in combination, hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, hydrogen It may have a distillation column for fractionating the chemical product and obtaining the desired fraction.
The reaction format of the hydrotreating apparatus of the present invention can be a fixed bed system. Hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid twin parallel flow format. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.
A kerosene oil fraction produced by the production process having at least one process selected from the Fischer-Tropsch synthesis process, the hydrocracking process of the wax-containing component, and the hydrorefining process of the component obtained from these processes as described above. Can be used as the hydrocarbon oil of the present invention.

The content of the metal working oil composition (B) a hydrocarbon oil of the present invention, the total amount of the composition 7 0 wt% or less, good Mashiku 60 mass% or less, more preferably 50 wt% or less . When the content exceeds 70% by mass, the oil mist characteristics are deteriorated, and when used for cutting / grinding with an extremely small amount of oil supply system, the working efficiency and tool life tend to be lowered. Moreover, content of (B) hydrocarbon oil is 5 mass% or more on the basis of the composition whole quantity, More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. When the content is less than 5 % by mass, an increase in welding or processing resistance in non-ferrous metal processing cannot be suppressed, and processing efficiency and tool life tend to decrease.

The metalworking oil composition of the present invention comprises (A) an ester oil and (B) a hydrocarbon oil, but may further contain other base oils.
Specific examples of the other base oils include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, polyoxyethylene polyoxypropylene glycol monoether, and polyethylene glycol diester. Polyglycols such as ether, polypropylene glycol diether, polyoxyethylene polyoxypropylene glycol diether; monoalkyl diphenyl ether, dialkyl diphenyl ether, monoalkyl triphenyl ether, dialkyl triphenyl ether, tetraphenyl ether, monoalkyl tetraphenyl ether, dialkyl Tetraphenyl ether, pentaphenyl ether Phenyl ether; silicone oil; fluoroether perfluoro ether, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of other base oils is preferably 65% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, based on the total amount of the composition. Preferably it is 10 mass% or less.

Moreover, it is preferable that the metalworking oil composition of this invention contains (C) oiliness agent from the point which processing efficiency and a tool life are raised more.
As the oily agent, (C-1) alcohol oily agent, (C-2) carboxylic acid oily agent, (C-3) sulfide of unsaturated carboxylic acid, (C-4) represented by the following general formula (1) (C-5) a compound represented by the following general formula (2), (C-6) a polyoxyalkylene compound, (C-7) an ester oily agent, (C-8) a polyhydric alcohol hydro Examples thereof include carbyl ether and (C-9) amine oily agent.

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

[In Formula (1), ^{R 1} represents a hydrocarbon group having 1 to 30 carbon atoms, a represents an integer of 1 to 6, b is an integer of 0-5. ]

［式（２）中、Ｒ^２は炭素数１〜３０の炭化水素基を表し、ｃは１〜６の整数を表し、ｄは０〜５の整数を表す。］

[In formula (2), ^{R 2} represents a hydrocarbon group having 1 to 30 carbon atoms, c is an integer of 1 to 6, d is an integer of 0-5. ]

  (C-1) The alcohol oil-based agent may be a monohydric alcohol or a polyhydric alcohol. A monohydric alcohol having 1 to 40 carbon atoms is preferable, higher alcohols having 1 to 25 carbon atoms are more preferable, and alcohols having 8 to 18 carbon atoms are most preferable in terms of obtaining higher processing efficiency and tool life. . Specifically, the example of the alcohol which comprises the ester of the said base oil can be given. These alcohols may be linear or branched, and may be saturated or unsaturated, but are preferably saturated from the viewpoint of anti-stickiness.

  (C-2) The carboxylic acid oily agent may be a monobasic acid or a polybasic acid. A monovalent carboxylic acid having 1 to 40 carbon atoms is preferable, higher carboxylic acid having 5 to 25 carbon atoms, and most preferably 5 to 20 carbon atoms from the viewpoint of obtaining higher processing efficiency and tool life. Carboxylic acid. Specifically, the example of the carboxylic acid which comprises the ester as said base oil can be given. 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.

  (C-3) Examples of the unsaturated carboxylic acid sulfide include unsaturated sulfides of the carboxylic acid (B). Specific examples include sulfides of oleic acid.

(C-4) In the compound represented by the general formula (1), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ include linear or branched alkyl having 1 to 30 carbon atoms, for example. Group, a C5-C7 cycloalkyl group, a C6-C30 alkyl cycloalkyl group, a C2-C30 linear or branched alkenyl group, a C6-C10 aryl group, a C7-C30 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. a is preferably an integer of 1 to 3, and more preferably 2. b is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (1) include p-tert-butylcatechol.

(C-5) In the compound represented by the general formula (2), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² are represented by R ¹ in the general formula (1). The same thing as the example of a C1-C30 hydrocarbon group made 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. c is preferably an integer of 1 to 3, and more preferably 2. d is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (2) include 2,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

  Examples of the (C-6) polyoxyalkylene compound include compounds represented by the following general formula (3) or (4).

_{^{R 3 O- (R 4 O)}} e -R 5 (3)
[In Formula (3), R ³ and R ⁵ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and e represents a number average molecular weight. Represents an integer such that 100 is 3500. ]
^{A - [(R 6 O)} f -R 7] g (4)
Wherein (3), A is hydroxyl represents 2.1-3.5 removing some or all of the hydrogen atoms of the hydroxyl groups of an alcohol having 3 to 10, R ⁶ is an alkylene group having 2 to 4 carbon atoms R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, f represents an integer having a number average molecular weight of 100 to 3500, and g represents the number of hydrogen atoms removed from the hydroxyl group of A. Represents the same number. ]

In the general formula (3), at least one of R ³ and R ⁵ is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ^5, for example, the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ in the general formula (1) Examples of preferred ones are also the same. Specific examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁴ include an ethylene group, a propylene group (methylethylene group), and a butylene group (ethylethylene group). e is preferably an integer such that the number average molecular weight is 300 to 2,000, and more preferably an integer such that the number average molecular weight is 500 to 1,500.

  Moreover, in the said General formula (4), as a specific example of the polyhydric alcohol which has 3-10 hydroxyl groups which comprise A, glycerin, polyglycerin (2-tetramer of glycerin, for example, diglycerin, triglycerin) , Tetraglycerin), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane) and their 2-tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3, 5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, idylitol, taritol, dulcitol, allitol Multivalent such as Alcohol; it xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, Mantosu, be mentioned Isomantosu, trehalose, and a saccharide such as sucrose. Among these, glycerin, polyglycerin, trimethylolalkane, and dimer to tetramer thereof, pentaerythritol, dipentaerythritol, sorbitol, or sorbitan are preferable.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁶ may be the same as the examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁴ in the general formula (3) . As examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁷ are given the same as examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ in the general formula (1) Examples of preferred ones are the same. At least one of g R ⁷ is preferably a hydrogen atom, more preferably all hydrogen atoms. f 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.

  As the (C-7) ester oily agent, the alcohol constituting it may be a monohydric alcohol or a polyhydric alcohol, and the carboxylic acid may be a monobasic acid or a polybasic acid. In addition, ester here is distinguished from the triester which is an essential component of the metalworking oil composition of this invention. In the following description, for the sake of convenience, the former is referred to as “ester oily agent”.

  Examples of the monohydric alcohol and polyhydric alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol, and the acid constituting the ester oily agent may be a monobasic acid or a polybasic acid. Good.

  As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, and saturated. Or may be unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecane Decanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol, linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as linear or branched tetracosanol, and mixtures thereof.

  As the polyhydric alcohol, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof That.

  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, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, and a mixture thereof are most preferable because higher thermal and oxidation stability can be obtained.

  As described above, the alcohol constituting the ester oil-based agent may be a monohydric alcohol or a polyhydric alcohol, but achieves excellent machining efficiency and tool life by preventing welding and increase in machining resistance. Polyhydric alcohols are preferred from the viewpoints of being able to be produced and having a low pour point more easily and improving the handling in winter and cold regions. 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.

  Of the acids constituting the ester oily agent, as the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used. The fatty acid may be linear or branched, and may not be saturated. It may be saturated. 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 preventing welding and increase in processing resistance and achieving excellent processing efficiency and tool life, and from the viewpoint of handleability, in particular, saturated fatty acids having 3 to 20 carbon atoms and those having 3 to 22 carbon atoms. Unsaturated fatty acids and mixtures thereof are preferable, saturated fatty acids having 4 to 18 carbon atoms, unsaturated fatty acids having 4 to 18 carbon atoms and mixtures thereof are more preferable, unsaturated fatty acids having 4 to 18 carbon atoms are more preferable, and stickiness From the standpoint of prevention, a saturated fatty acid having 4 to 18 carbon atoms is more 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.

  The combination of an alcohol and an acid in the ester oily agent is arbitrary and not particularly limited. Examples of the ester oily agent that can be used in the present invention include the following esters.

(C-7-1) ester of monohydric alcohol and monobasic acid (C-7-2) ester of polyhydric alcohol and monobasic acid (C-7-3) of monohydric alcohol and polybasic acid Esters (C-7-4) Esters of polyhydric alcohols and polybasic acids (C-7-5) Mixed esters of monohydric alcohols, mixtures of polyhydric alcohols and polybasic acids (C-7-6) Mixed ester of polyhydric alcohol and monobasic acid, mixture of polybasic acid (G-7-7) Monohydric alcohol, mixture of polyhydric alcohol and monobasic acid, mixed ester of 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 oily agent is not particularly limited, but an ester having a total carbon number of 7 or more is preferable from the viewpoint of preventing welding and an increase in processing resistance and achieving excellent processing efficiency and tool life. 9 or more esters are more preferred, and 11 or more esters are 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.

  (C-8) The polyhydric alcohol constituting the hydrocarbyl ether of the polyhydric alcohol is usually 2 to 10 valent, preferably 2 to 6 valent. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof That.

  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 because it can prevent welding and increase in processing resistance to achieve excellent processing efficiency and tool life.

  (C-8) As the hydrocarbyl ether of a 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. A point that can achieve excellent machining efficiency and tool life by preventing welding and increase in machining resistance Polyhydric alcohol from the point that it can achieve excellent machining efficiency and tool life by preventing welding and increase in machining resistance Those obtained by hydrocarbyl etherifying a part of the hydroxyl groups of (a partially etherified product) are preferred. 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.

  Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, linear or branched pentyl. Group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or Branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group , Linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear or branched Branched docosyl group, linear or branched tri Sill group, such as a straight-chain or branched tetracosyl groups.

  Examples of the alkenyl group having 2 to 24 carbon atoms include a vinyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, and a linear or branched hexenyl group. Linear or branched heptenyl group, linear or branched octenyl group, linear or branched nonenyl group, linear or branched decenyl group, linear or branched undecenyl group, linear or branched A branched dodecenyl group, a linear or branched tridecenyl group, a linear or branched tetradecenyl group, a linear or branched pentadecenyl group, a linear or branched hexadecenyl group, a linear or branched heptadecenyl group, Linear or branched octadecenyl group, linear or branched nonadecenyl group, linear or branched icocenyl group, linear or branched henicosenyl group, linear or branched dococenyl group, linear or branched Tricosenyl group, straight chain The like tetracosenyl group branched thereof.

  Examples of the cycloalkyl group having 5 to 7 carbon atoms include cyclpentyl group, cyclohexyl group, and cycloheptyl group. Examples of the alkylcycloalkyl group having 6 to 11 carbon atoms include methylcyclopentyl group, dimethylcyclopentyl group (including all structural isomers), methylethylcyclopentyl group (including all structural isomers), and diethylcyclopentyl group ( Including all structural isomers), methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (all structures) Isomers), methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (including all structural isomers), diethylcycloheptyl group (all Including structural isomers).

  Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the alkylaryl group having 7 to 18 carbon atoms include a tolyl group (including all structural isomers), a xylyl group (including all structural isomers), and an ethylphenyl group (including all structural isomers). ), Linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl A group (including all structural isomers), a linear or branched hexylphenyl group (including all structural isomers), a linear or branched heptylphenyl group (including all structural isomers). ), Linear or branched octylphenyl group (including all structural isomers), linear or branched nonylphenyl group (including all structural isomers), linear or branched decylphenyl Group (including all structural isomers), linear or Undecylphenyl branches (including all structural isomers.) (Including all structural isomers.) Linear or branched dodecylphenyl group and the like.

  Examples of the arylalkyl group having 7 to 12 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group (including propyl group isomers), phenylbutyl group (including butyl group isomers), and phenylpentyl group ( Pentyl group isomers), phenylhexyl group (including hexyl isomers), and the like.

  Among these, a linear or branched alkyl group having 2 to 18 carbon atoms or a carbon number having 2 to 18 carbon atoms from the viewpoint of preventing welding and increase in processing resistance and achieving excellent machining efficiency and tool life. A linear or branched alkenyl group is preferable, and a linear or branched alkyl group having 3 to 12 carbon atoms and an oleyl group (residue obtained by removing a hydroxyl group from oleyl alcohol) are more preferable.

  As the (C-9) amine oily agent, monoamine is preferably used. 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 monoamine. When the monoamine has two or more hydrocarbon groups, it represents the total number of carbon atoms.

  As the monoamine used in the present invention, any of primary monoamine, secondary monoamine, and tertiary monoamine can be used. A primary monoamine is preferable from the viewpoint that the lifetime can be achieved.

  As the hydrocarbon group bonded to the nitrogen atom of the monoamine, any of an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, etc. can be used. In view of preventing the increase in machining resistance and achieving excellent machining efficiency and tool life, an alkyl group or an alkenyl group is preferred. The alkyl group or alkenyl group may be linear or branched, but it can prevent welding and increase in processing resistance and improve processing efficiency and tool life. A linear one is preferred.

  Preferable monoamines used in the present invention include, for example, hexylamine (including all isomers), heptylamine (including all isomers), and octylamine (including all isomers). , Nonylamine (including all isomers), decylamine (including all isomers), undecylamine (including all isomers), dodecylamine (including all isomers), tridecylamine (all Including isomers), tetradecylamine (including all isomers), pentadecylamine (including all isomers), hexadecylamine (including all isomers), heptadecylamine (all isomers) ), Octadecylamine (including all isomers), nonadecylamine (including all isomers), icosylamine (including all isomers), hen Cosylamine (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, a primary monoamine having 12 to 24 carbon atoms is preferable, and a primary monoamine having 14 to 20 carbon atoms is preferable because it can prevent welding and increase in processing resistance to achieve excellent processing efficiency and tool life. Monoamines are more preferable, and primary monoamines having 16 to 18 carbon atoms are more preferable.

  In this invention, only 1 type chosen from the said oil-based agent (C-1)-(C-9) may be used, and 2 or more types of mixtures may be used. Among these, 1 selected from (C-2) carboxylic acid oil agent and (C-9) amine oil agent from the viewpoint of preventing welding and increase in machining resistance and achieving excellent machining efficiency and tool life. It is preferably a seed or a mixture of two or more.

  (C) The content of the oily agent is not particularly limited, but is preferably 0.01 on the basis of the total amount of the composition because it can prevent welding and increase in processing resistance and achieve excellent processing efficiency and tool life. It is at least mass%, more preferably at least 0.05 mass%, still more preferably at least 0.1 mass%. From the viewpoint of stability, the content of the oily agent is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, based on the total amount of the composition.

  Moreover, it is preferable that the metalworking oil composition of this invention further contains (D) extreme pressure agent from the point which can prevent welding and the increase in processing resistance and can achieve the outstanding processing efficiency and tool life. In particular, when (D) the extreme pressure agent is used in combination with the above-described (C) oily agent, these synergistic effects can prevent welding and increase in processing resistance and achieve further excellent processing efficiency and tool life. It becomes possible. Moreover, although the metalworking oil composition of this invention can be used as lubricating oil other than the process part of a machine tool so that it may mention later, in this case, it may contain (C) oiliness agent. desirable.

  Examples of (D) extreme pressure agents include (D-1) sulfur compounds and (D-2) phosphorus compounds described later.

  (D-1) The sulfur compound is not particularly limited as long as it does not impair the properties of the metalworking oil composition, but dihydrocarbyl polysulfide, sulfide ester, sulfide mineral oil, zinc dithiophosphate, zinc dithiocarbamate, dithiophosphorus A molybdenum acid compound and molybdenum dithiocarbamate are preferably used.

Dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin. Specifically, the following general formula (5):
_{^{R 8 -S h -R 9 (5}} )
[In Formula (5), R ⁸ and R ⁹ 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. Represents an alkylaryl group having 6 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms, and h represents an integer of 2 to 6, preferably 2 to 5.]
The compound represented by these is meant. As R ⁸ and R ⁹ in the general formula (5), specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched Undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group Linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched alkyl group such as linear or branched icosyl group; aryl group such as phenyl group or naphthyl group; tolyl group ( Including all structural isomers), et Ruphenyl group (including all structural isomers), linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear Or branched pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (including all structural isomers) ), Linear or branched octylphenyl groups (including all structural isomers), linear or branched nonylphenyl groups (including all structural isomers), linear or branched decylphenyl groups (all structures) Isomers), linear or branched undecylphenyl groups (including all structural isomers), linear or branched dodecylphenyl groups (including all structural isomers), xylyl groups (all structural isomers) Body), ethyl methyl Enyl group (including all structural isomers), diethylphenyl group (including all structural isomers), di (straight or branched) propylphenyl group (including all structural isomers), di (linear) Or branched) butylphenyl group (including all structural isomers), methyl naphthyl group (including all structural isomers), ethyl naphthyl group (including all structural isomers), linear or branched propyl naphthyl Group (including all structural isomers), linear or branched butyl naphthyl group (including all structural isomers), dimethyl naphthyl group (including all structural isomers), ethyl methyl naphthyl group (all structures) Isomers), diethyl naphthyl group (including all structural isomers), di (straight or branched) propyl naphthyl group (including all structural isomers), di (straight or branched) butyl naphthyl Group (all structural differences Alkylaryl groups, such as including the body); and the like; benzyl group include phenyl ethyl (all isomers), including phenylpropyl group (all isomers) arylalkyl groups, such as. Among them, R ⁸ and R ⁹ in the general formula (5), propylene, 1-butene or an alkyl group has been 3 to 18 carbon atoms derived from isobutylene, or an aryl group having a carbon number of 6-8, alkyl An aryl group or an arylalkyl group is preferable. Examples of these groups include isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), and propylene trimer. Branched nonyl groups derived from the body (including all branched isomers), branched dodecyl groups derived from the propylene tetramer (including all branched isomers), 5 quantities of propylene Branched pentadecyl groups derived from the body (including all branched isomers), branched octadecyl groups derived from the propylene hexamer (including all branched isomers), sec Branched octyl group derived from butyl group, tert-butyl group, 1-butene dimer (including all branched isomers), branched octyl group derived from isobutylene dimer (all ), Branched dodecyl groups derived from 1-butene trimer (including all branched isomers), branched dodecyl groups derived from isobutylene trimer (Including all branched isomers), branched hexadecyl group derived from 1-butene tetramer (including all branched isomers), branched derived from isobutylene tetramer Alkyl groups such as hexadecyl group (including all branched isomers); phenyl group, tolyl group (including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (all (Including structural isomers) Groups; arylalkyl groups such as benzyl group and phenylethyl group (including all isomers).

Furthermore, R ⁸ and R ⁹ in the above general formula (5) are separately derived from ethylene or propylene because they can prevent welding and increase in processing resistance to achieve excellent processing efficiency and tool life. The branched alkyl group having 3 to 18 carbon atoms is more preferable, and the branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene is particularly preferable.

  Specific examples of the sulfur ester include animal and vegetable fats and oils such as beef tallow, pork tallow, fish tallow, rapeseed oil and soybean oil; unsaturated fatty acids (oleic acid, linoleic acid or fatty acids extracted from the above-mentioned animal and plant fats and the like) And an unsaturated fatty acid ester obtained by reacting various alcohols with each other; and a mixture thereof obtained by sulfiding by an arbitrary method.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited. Specifically, specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is used as a solvent. Examples thereof include paraffinic mineral oil, naphthenic mineral oil, and the like, which are refined by appropriately combining purification treatments such as deblocking, solvent extraction, hydrocracking, 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 the sulfur content in the sulfide mineral oil concerning this invention, 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% by mass.

  The zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate compound and the molybdenum dithiocarbamate compound are represented by the following general formulas (6) to (9):

［式（６）〜（９）中、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、Ｒ^２４及びＲ^２５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及びＸ^２はそれぞれ酸素原子又は硫黄原子を表す］
で表される化合物を意味する。

[In the formulas (6) to (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 , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ¹ and X ² each represent an oxygen atom or a sulfur atom]
The compound represented by these is meant.

Here, 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 , R ²⁴ and R ²⁵ Specific examples of the hydrocarbon group represented by: methyl group, ethyl group, propyl group (including all branched isomers), butyl group (including all branched isomers), pentyl group (including Including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers), nonyl Groups (including all branched isomers), decyl groups (including all branched isomer pairs), undecyl groups (including all branched isomer pairs), dodecyl groups (including all branched isomer pairs) , Tridecyl group (including all branched pairs), tetradec Groups (including all branched isomer pairs), pentadecyl groups (including all branched isomer pairs), hexadecyl groups (including all branched isomer pairs), heptadecyl groups (including all branched isomer pairs) , Octadecyl group (including all branched isomer pairs), nonadecyl group (including all branched isomer pairs), icosyl group (including all branched isomer pairs), heicosyl group (including all branched isomer pairs) Alkyl groups such as docosyl groups (including all branched isomer pairs), tricosyl groups (including all branched isomer pairs), tetracosyl groups (including all branched isomer pairs); cyclopentyl groups, cyclohexyl Group, cycloalkyl group such as cycloheptyl group; methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethyl Clopentyl group (including all substituted isomers), propylcyclopentyl group (including all branched isomers, including substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers) Substituted isomers), butylcyclopentyl group (all branched isomers, including substituted isomers), methylpropylcyclopentyl group (including all branched isomers, substituted isomers), diethylcyclopentyl group (all Substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (Including all substituted isomers), propylcyclohexyl groups (all Branched isomers, including substituted isomers, methylethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), butylcyclohexyl group (all branched isomers, Substituted isomers), methylpropylcyclohexyl group (including all branched isomers, including substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers) ), Methylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (including All branched isomers, including substituted isomers), methylethylcycloheptyl group (all substituted isomers) ), Trimethylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (including all branched isomers, including substituted isomers), methylpropylcycloheptyl group (including all branched isomers), Substituted isomers), diethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers) and other alkyl cycloalkyl groups; phenyl group, naphthyl group and other aryls Group; tolyl group (including all substituted isomers), xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (all branched isomers, Substituted isomers), methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers) ), Butylphenyl group (including all branched and substituted isomers), methylpropylphenyl group (including all branched and substituted isomers), and diethylphenyl group (including all substituted isomers) Dimethylethylphenyl group (including all substituted isomers), pentylphenyl group (including all branched isomers, including substituted isomers), hexylphenyl group (including all branched isomers, substituted isomers) ), Heptylphenyl group (including all branched isomers, substituted isomers), octylphenyl group (including all branched isomers, substituted isomers), nonylphenyl group (all branched isomers, Substituted isomers), decylphenyl group (including all branched isomers, including substituted isomers), undecylphenyl group (including all branched isomers, including substituted isomers), dodecylphenyl Group (including all branched isomers, substituted isomers), tridecylphenyl group (including all branched isomers, substituted isomers), tetradecylphenyl group (all branched isomers, substituted isomers) ), Pentadecylphenyl group (including all branched and substituted isomers), hexadecylphenyl group (including all branched and substituted isomers), heptadecylphenyl group (including all branched isomers) Alkylaryl groups such as branched isomers, including substituted isomers, octadecylphenyl groups (including all branched isomers and substituted isomers); benzyl groups, phenethyl groups, phenylpropyl groups (all branched isomers) And arylalkyl groups such as phenylbutyl group (including all branched isomers).

  In the present invention, among the above sulfur compounds, when at least one selected from the group consisting of dihydrocarbyl polysulfide and sulfurized ester is used, it is possible to prevent welding and increase in processing resistance and to achieve a higher level of processing efficiency and This is preferable because the tool life can be achieved.

  Specific examples of the phosphorus compound (D-2) include phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters, and phosphorothioates. And metal salts of phosphorus compounds represented by the following general formula (10) or (11). Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof.

［式（１０）中、Ｘ^３、Ｘ^４及びＸ^５は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を表し、Ｘ^３、Ｘ^４又はＸ^５の少なくとも２つは酸素原子であり、Ｒ^２６、Ｒ^２７、及びＲ^２８は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を表す］

[In Formula (10), X ³ , X ⁴ and X ⁵ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least two of X ³ , X ⁴ or X ⁵ are oxygen atoms; , R ²⁶ , R ²⁷ , and R ²⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms]

［式（１１）中、Ｘ^６、Ｘ^７、Ｘ^８及びＸ^９は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を表し、Ｘ^６、Ｘ^７、Ｘ^８又はＸ^９の少なくとも３つは酸素原子であり、Ｒ^２９、Ｒ^３０及びＲ^３１は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を表す。］
より具体的には、リン酸エステルとしては、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリヘプチルホスフェート、トリオクチルホスフェート、トリノニルホスフェート、トリデシルホスフェート、トリウンデシルホスフェート、トリドデシルホスフェート、トリトリデシルホスフェート、トリテトラデシルホスフェート、トリペンタデシルホスフェート、トリヘキサデシルホスフェート、トリヘプタデシルホスフェート、トリオクタデシルホスフェート、トリオレイルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート等；
酸性リン酸エステルとしては、モノブチルアシッドホスフェート、モノペンチルアシッドホスフェート、モノヘキシルアシッドホスフェート、モノヘプチルアシッドホスフェート、モノオクチルアシッドホスフェート、モノノニルアシッドホスフェート、モノデシルアシッドホスフェート、モノウンデシルアシッドホスフェート、モノドデシルアシッドホスフェート、モノトリデシルアシッドホスフェート、モノテトラデシルアシッドホスフェート、モノペンタデシルアシッドホスフェート、モノヘキサデシルアシッドホスフェート、モノヘプタデシルアシッドホスフェート、モノオクタデシルアシッドホスフェート、モノオレイルアシッドホスフェート、ジブチルアシッドホスフェート、ジペンチルアシッドホスフェート、ジヘキシルアシッドホスフェート、ジヘプチルアシッドホスフェート、ジオクチルアシッドホスフェート、ジノニルアシッドホスフェート、ジデシルアシッドホスフェート、ジウンデシルアシッドホスフェート、ジドデシルアシッドホスフェート、ジトリデシルアシッドホスフェート、ジテトラデシルアシッドホスフェート、ジペンタデシルアシッドホスフェート、ジヘキサデシルアシッドホスフェート、ジヘプタデシルアシッドホスフェート、ジオクタデシルアシッドホスフェート、ジオレイルアシッドホスフェート等；
酸性リン酸エステルのアミン塩としては、前記酸性リン酸エステルのメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリヘプチルアミン、トリオクチルアミン等のアミンとの塩等；
塩素化リン酸エステルとしては、トリス・ジクロロプロピルホスフェート、トリス・クロロエチルホスフェート、トリス・クロロフェニルホスフェート、ポリオキシアルキレン・ビス［ジ（クロロアルキル）］ホスフェート等；
亜リン酸エステルとしては、ジブチルホスファイト、ジペンチルホスファイト、ジヘキシルホスファイト、ジヘプチルホスファイト、ジオクチルホスファイト、ジノニルホスファイト、ジデシルホスファイト、ジウンデシルホスファイト、ジドデシルホスファイト、ジオレイルホスファイト、ジフェニルホスファイト、ジクレジルホスファイト、トリブチルホスファイト、トリペンチルホスファイト、トリヘキシルホスファイト、トリヘプチルホスファイト、トリオクチルホスファイト、トリノニルホスファイト、トリデシルホスファイト、トリウンデシルホスファイト、トリドデシルホスファイト、トリオレイルホスファイト、トリフェニルホスファイト、トリクレジルホスファイト等；
フォスフォロチオネートとしては、トリブチルフォスフォロチオネート、トリペンチルフォスフォロチオネート、トリヘキシルフォスフォロチオネート、トリヘプチルフォスフォロチオネート、トリオクチルフォスフォロチオネート、トリノニルフォスフォロチオネート、トリデシルフォスフォロチオネート、トリウンデシルフォスフォロチオネート、トリドデシルフォスフォロチオネート、トリトリデシルフォスフォロチオネート、トリテトラデシルフォスフォロチオネート、トリペンタデシルフォスフォロチオネート、トリヘキサデシルフォスフォロチオネート、トリヘプタデシルフォスフォロチオネート、トリオクタデシルフォスフォロチオネート、トリオレイルフォスフォロチオネート、トリフェニルフォスフォロチオネート、トリクレジルフォスフォロチオネート、トリキシレニルフォスフォロチオネート、クレジルジフェニルフォスフォロチオネート、キシレニルジフェニルフォスフォロチオネート、トリス（ｎ−プロピルフェニル）フォスフォロチオネート、トリス（イソプロピルフェニル）フォスフォロチオネート、トリス（ｎ−ブチルフェニル）フォスフォロチオネート、トリス（イソブチルフェニル）フォスフォロチオネート、トリス（ｓ−ブチルフェニル）フォスフォロチオネート、トリス（ｔ−ブチルフェニル）フォスフォロチオネート等
が挙げられる。

[In formula (11), X ⁶ , X ⁷ , X ⁸ and X ⁹ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least 3 of X ⁶ , X ⁷ , X ⁸ or X ⁹ One is an oxygen atom, and R ²⁹ , R ³⁰ and R ³¹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]
More specifically, the phosphate ester includes tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl Phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyl Renyl diphenyl phosphate and the like;
Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, etc .;
Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, etc .;
Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like;
As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite etc .;
The phosphorothioates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothioate, tritridecyl phosphorothioate, tritetradecyl phosphorothioate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate , Triheptadecyl phosphorothioate, trioctadecyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tri Resyl phosphorothioate, trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phos Phosphorothionate, tris (n-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. Is mentioned.

Moreover, regarding the metal salt of the phosphorus compound represented by the general formula (10) or (11), the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{26 to} R ³¹ in the formula is specifically Includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

  Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like. Group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups may be linear or branched).

  As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example. Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include an alkylcycloalkyl group having 6 to 11 carbon atoms such as a dimethylcycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).

  Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also optional).

  As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example. Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl. Group, an alkylaryl group having 7 to 18 carbon atoms such as undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is arbitrary). .

  Examples of the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group. It may be branched).

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{26 to} R ³¹ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 3 carbon atoms. An alkyl group having 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

R ²⁶ , R ²⁷ and R ²⁸ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group, and among R ²⁶ , R ²⁷ and R ²⁸ , 1 to 3 are the above hydrocarbon groups. It is preferable that 1 to 2 is the above hydrocarbon group, and more preferably 2 is the above hydrocarbon group.

R ²⁹ , R ³⁰ and R ³¹ may be the same or different and each represents a hydrogen atom or the above hydrocarbon group. Among R ²⁹ , R ³⁰ and R ³¹ , 1 to 3 are the above hydrocarbons. It is preferably a group, 1 to 2 are more preferably the hydrocarbon group, and 2 are more preferably the hydrocarbon group.

In the general formula (10) phosphorus compounds represented by, at least two of X ³ to X ⁵ is required to be an oxygen atom, that all X ³ to X ⁵ is an oxygen atom preferable.

In the phosphorus compound represented by the general formula (11), at least three of X ^{6 to} X ⁹ are required to be oxygen atoms, but all of X ^{6 to} X ⁹ are oxygen atoms. It is preferable.

  Examples of the phosphorus compound represented by the general formula (10) include phosphorous acid and monothiophosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms and monothiophosphorous acid mono Ester; Phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester; Phosphorous acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid Acid triesters; and mixtures thereof. Among these, phosphorous acid monoester and phosphorous acid diester are preferable, and phosphorous acid diester is more preferable.

  Examples of the phosphorus compound represented by the general formula (11) include phosphoric acid and monothiophosphoric acid; phosphoric acid monoester and monothiophosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; And phosphoric acid diesters and monothiophosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; phosphoric acid triesters and monothiophosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. It is done. Among these, phosphoric acid monoester and phosphoric acid diester are preferable, and phosphoric acid diester is more preferable.

  Examples of the metal salt of the phosphorus compound represented by the general formula (10) or (11) include a salt obtained by neutralizing part or all of the acidic hydrogen of the phosphorus compound with a metal base. Examples of such metal bases include metal oxides, metal hydroxides, metal carbonates, metal chlorides and the like. Specific examples of the metal include alkali metals such as lithium, sodium, potassium, cesium, and calcium. And alkaline earth metals such as magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  The metal salt of the phosphorus compound has a different structure depending on the valence of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid diester ( When 2 mol of 1 OH group is reacted, it is considered that a compound having a structure represented by the following formula (12) is obtained as a main component, but it is also considered that polymerized molecules exist.

また、例えば、酸化亜鉛１ｍｏｌとリン酸モノエステル（ＯＨ基が２つ）１ｍｏｌとを反応させた場合、下記式（１３）で表される構造の化合物が主成分として得られると考えられるが、ポリマー化した分子も存在していると考えられる。

In addition, for example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (two OH groups) are reacted, a compound having a structure represented by the following formula (13) is considered to be obtained as a main component. Polymerized molecules are also thought to exist.

また、これらの２種以上の混合物も使用できる。

A mixture of two or more of these can also be used.

  In the present invention, among the above phosphorous compounds, phosphoric acid esters, acidic phosphoric acid esters, and acidic phosphoric acid esters can be achieved from preventing welding and increasing processing resistance and achieving excellent processing efficiency and tool life. Amine salts are preferred.

  Further, as described later, the metalworking oil composition of the present invention is applicable to uses other than metalworking, but the metalworking oil composition of the present invention is used as a sliding surface oil for machine tools. It is preferable to contain acidic phosphate ester and amine salt of acidic phosphate ester. Moreover, when using the metalworking oil composition of this invention as a hydraulic fluid, phosphate ester is preferable. Further, when used as a combined oil for sliding surface oil and hydraulic fluid, at least one selected from acidic phosphate esters and amine salts of acidic phosphate esters and a phosphate ester are used in combination. It is preferable.

  The metalworking oil composition of the present invention may contain only one of (D-1) a sulfur compound or (D-2) a phosphorus compound, or may contain both. From the viewpoint of preventing welding and increase in machining resistance and achieving excellent machining efficiency and tool life, (D-1) phosphorus compound, or (D-1) sulfur compound and (D-2) phosphorus compound It is preferable to contain both, and it is more preferable to contain both (D-1) sulfur compound and (D-2) phosphorus compound.

  (D) The content of the extreme pressure agent is arbitrary, but 0.005% by mass based on the total amount of the composition from the viewpoint of achieving excellent machining efficiency and tool life by preventing welding and increase in machining resistance. Preferably, it is 0.01% by mass or more, and more preferably 0.05% by mass or more. From the viewpoint of preventing abnormal wear, the content of the extreme pressure agent is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 7% by mass or less, based on the total amount of the composition. Even more preferably.

  In the present invention, only one of the above-mentioned (C) oily agent or (D) extreme pressure agent may be used, but excellent machining efficiency and tool life can be achieved by preventing welding and increase in machining resistance. In view of this, it is preferable to use (C) an oily agent and (D) an extreme pressure agent in combination.

  Moreover, in the metalworking oil composition of this invention, it is preferable to contain (E) organic acid salt from the point which can prevent welding and the increase in processing resistance and can achieve the outstanding processing efficiency and tool life. 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.

  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 by-produced during white oil production, 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 And synthetic sulfonic acids such as those obtained by sulphonation of sulphonate. 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; neutral (normal salt) sulfonates with alkali React with genus bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) sulfonates with boric acid or boric anhydride And so-called borate overbased (superbasic) sulfonates produced by reacting boric 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.

  (E) The base number of the organic acid salt is preferably 50 to 500 mgKOH / g, more preferably 100 to 450 mgKOH / g. When the 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 base number exceeding 500 mgKOH / g is usually Each is not preferable because it is very difficult to manufacture and difficult to obtain. The base number referred to here is 7. JIS K 2501 “Petroleum products and lubricants—neutralization number test method”. The base number [mgKOH / g] by the perchloric acid method measured according to the above.

  In addition, the content of the (E) 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 based on the total amount of the composition. % By mass. (E) When the content of the organic acid salt is less than the lower limit, the effect of improving machining efficiency and tool life due to prevention of welding and increase in machining resistance due to the addition tends to be insufficient, When the upper limit is exceeded, the stability of the metalworking oil composition tends to be lowered and precipitates tend to occur.

  In the present invention, (E) an organic acid salt may be used alone, or an organic acid salt and another additive may be used in combination. From the viewpoint of preventing welding and increase in machining resistance and achieving excellent machining efficiency and tool life, it is preferable to use organic acid salts in combination with the above extreme pressure agents, sulfur compounds, phosphorus compounds and organic acids. It is particularly preferable to use a combination of three salts.

  Moreover, it is preferable that the metalworking oil composition of this invention further contains (F) 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.

  Examples of (F) antioxidants include phenolic antioxidants, amine antioxidants, zinc dithiophosphate antioxidants, and those used as food additives.

  As the phenolic antioxidant, any phenolic compound used as an antioxidant for lubricating oil can be used, and is not particularly limited. For example, the following general formulas (14) and (15) are used. One type or two or more types of alkylphenol compounds selected from the compounds represented by formula (1) are preferred.

［式（１４）中、Ｒ^３２は炭素数１〜４のアルキル基を示し、Ｒ^３３は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^３４は水素原子、炭素数１〜４のアルキル基、下記一般式（ｉ）又は（ｉｉ）：

[In the formula (14), R ³² represents an alkyl group having 1 to 4 carbon atoms, R ³³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group, the following general formula (i) or (ii):

（一般式（ｉ）中、Ｒ^３５は炭素数１〜６のアルキレン基を示し、Ｒ^３６は炭素数１〜２４のアルキル基又はアルケニル基を示す。）

(In the general formula (i), R ³⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ³⁶ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms.)

（一般式（ｉｉ）中、Ｒ^３７は炭素数１〜６のアルキレン基を示し、Ｒ^３８は炭素数１〜４のアルキル基を示し、Ｒ^３９は水素原子又は炭素数１〜４のアルキル基を示し、ｋは０又は１を示す。）
で表される基を示す。］

(In the general formula (ii), R ³⁷ represents an alkylene group having 1 to 6 carbon atoms, R ³⁸ represents an alkyl group having 1 to 4 carbon atoms, and R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And k represents 0 or 1.)
The group represented by these is shown. ]

［一般式（１５）中、Ｒ^４０及びＲ^４２は同一でも異なっていてもよく、それぞれ炭素数１〜４のアルキル基を示し、Ｒ^４１及びＲ^４３は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^４４及びＲ^４５は同一でも異なっていてもよく、それぞれ炭素数１〜６のアルキレン基を示し、Ａは炭素数１〜１８のアルキレン基又は下記の一般式（ｉｉｉ）：
−Ｒ^４６−Ｓ−Ｒ^４７− （ｉｉｉ）
（一般式（ｉｉｉ）中、Ｒ^４６及びＲ^４７は同一でも異なっていてもよく、それぞれ炭素数１〜６のアルキレン基を示す）
で表される基を示す。］
本発明に使用されるアミン系酸化防止剤としては、潤滑油の酸化防止剤として用いられる任意のアミン系化合物が使用可能であり、特に限定されるものではないが、例えば、下記の一般式（１６）で表されるフェニル−α−ナフチルアミン又はＮ−ｐ−アルキルフェニル−α−ナフチルアミン、並びに下記一般式（１７）で表されるｐ，ｐ’−ジアルキルジフェニルアミンの中から選ばれる１種又は２種以上の芳香族アミンが好ましいものとして挙げられる。

[In General Formula (15), R ⁴⁰ and R ⁴² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms; R ⁴¹ and R ⁴³ may be the same or different; Represents an atom or an alkyl group having 1 to 4 carbon atoms, R ⁴⁴ and R ⁴⁵ may be the same or different, each represents an alkylene group having 1 to 6 carbon atoms, and A represents an alkylene group having 1 to 18 carbon atoms or The following general formula (iii):
-R ⁴⁶ -S-R ^47- (iii)
(In the general formula (iii), R ⁴⁶ and R ⁴⁷ may be the same or different and each represents an alkylene group having 1 to 6 carbon atoms)
The group represented by these is shown. ]
As the amine-based antioxidant used in the present invention, any amine-based compound used as an antioxidant for lubricating oil can be used, and is not particularly limited. For example, the following general formula ( 16) One or two selected from phenyl-α-naphthylamine or Np-alkylphenyl-α-naphthylamine represented by 16) and p, p′-dialkyldiphenylamine represented by the following general formula (17) More than one type of aromatic amine is preferred.

［式（１６）中、Ｒ^４８は水素原子又はアルキル基を示す。］

[In the formula (16), R ⁴⁸ represents a hydrogen atom or an alkyl group. ]

［式（１７）中、Ｒ^４９及びＲ^５０は同一でも異なっていてもよく、それぞれアルキル基を示す。］
アミン系酸化防止剤の具体例としては、４−ブチル−４’−オクチルジフェニルアミン、フェニル−α−ナフチルアミン、オクチルフェニル−α−ナフチルアミン、ドデシルフェニル−α−ナフチルアミン及びこれらの混合物などが挙げられる。

[In formula (17), R ⁴⁹ and R ⁵⁰ may be the same or different and each represents an alkyl group. ]
Specific examples of the amine antioxidant include 4-butyl-4′-octyldiphenylamine, phenyl-α-naphthylamine, octylphenyl-α-naphthylamine, dodecylphenyl-α-naphthylamine, and mixtures thereof.

Specific examples of the zinc dithiophosphate antioxidant used in the present invention include zinc dithiophosphate represented by the following general formula (14).

［式（１４）中、Ｒ^５１、Ｒ^５２、Ｒ^５３及びＲ^５４は同一でも異なっていてもよく、それぞれ炭化水素基を示す。］
また、食品添加剤として使用されている酸化防止剤も使用可能であり、上述したフェノール系酸化防止剤と一部重複するが、例えば、例えば、２，６−ジ−tert−ブチル−ｐ−クレゾール（ＤＢＰＣ）、４，４’−メチレンビス（２，６−ジ−tert−ブチルフェノール）、４，４’−ビス（２，６−ジ−tert−ブチルフェノール）、４，４’−チオビス（６−tert−ブチル−ｏ−クレゾール）、アスコルビン酸（ビタミンＣ）、アスコルビン酸の脂肪酸エステル、トコフェロール（ビタミンＥ）、３，５−ジ−tert−ブチル−４−ヒドロキシアニソール、２−tert−ブチル−４−ヒドロキシアニソール、３−tert−ブチル−４−ヒドロキシアニソール、１，２−ジハイドロ−６−エトキシ−２，２，４−トリメチルキノリン（エトキシキン）、２−（１，１−ジメチル）−１，４−ベンゼンジオール（ＴＢＨＱ）、２，４，５−トリヒドロキシブチロフェノン（ＴＨＢＰ）を挙げることができる。

[In formula (14), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different and each represents a hydrocarbon group. ]
Further, an antioxidant used as a food additive can also be used, and partially overlaps with the above-described phenolic antioxidant. 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-trimethylquinoline (ethoxyquin), 2- (1,1 -Dimethyl) -1,4-benzenediol (TBHQ), 2,4,5-trihydroxybutyrophenone (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, tocopherol (Vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC), or 3,5-di-tert-butyl-4-hydroxyanisole is more preferred.

  (F) Although there is no restriction | limiting in particular in content of antioxidant, In order to maintain favorable heat | fever and oxidation stability, the content is 0.01 mass% or more on the basis of the composition whole quantity, More preferably 0.05 mass% or more, most preferably 0.1 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.

  Moreover, the metalworking oil composition of the present invention 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 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 amine Emissions, 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 is added in such an amount that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the composition. It is common.

  In addition, although the metalworking oil composition of the present invention may contain a chlorine-based additive such as a chlorine-based extreme pressure agent as described above, from the viewpoint of improving safety and reducing the burden on the environment, 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 composition. It is particularly preferred.

Although the kinematic viscosity of the metalworking oil composition of the present invention is not particularly limited, the kinematic viscosity at 40 ° C. is preferably 200 mm ² / s or less, and more preferably 100 mm ² from the viewpoint of easy supply to the processing site. / S, more preferably 75 mm ² / s, and most preferably 50 mm ² / s. On the other hand, the lower limit is preferably 1 mm ² / s, more preferably 3 mm ² / s, and most preferably 5 mm ² / s.

  Moreover, the water content of the metalworking oil composition of the present invention is preferably 20000 ppm or less, more preferably 10,000 ppm or less, and still more preferably 5000 ppm or less from the viewpoint of storage stability and rust prevention. In addition, the water content is preferably 200 ppm or more, more preferably 300 ppm or more, and even more preferably 400 ppm or more, from the viewpoint that excellent machining efficiency and tool life can be achieved by preventing welding and increase in machining resistance. Preferably it is 500 ppm or more.

  In addition, the water content as used in the field of this invention means the water content measured by the Karl Fischer-type coulometric titration method based on JIS K2275.

  In addition, when adjusting the water content by adding water to the metalworking oil composition of the present invention, the water to be added may be either hard water or soft water, such as tap water, industrial water, ion exchange water, distillation. Water, alkaline ionized water, etc. can be used arbitrarily.

  The metalworking oil composition of the present invention having the above configuration is excellent in processing performance such as processing efficiency, tool life, and handling properties, and can be suitably used in a wide range of applications in the metalworking field. . The metal processing here is not limited to cutting / grinding, but broadly means general metal processing.

  Moreover, although the metalworking oil composition of the present invention can be applied to metalworking by a normal refueling system, it exhibits a more remarkable effect, so that it is used as a processing oil in a micro-volume oil supply system (MQL). It is preferable.

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

  The material of the workpiece to which the metalworking oil composition of the present invention is applied is not particularly limited, but the metalworking oil composition of the present invention is suitable as a non-ferrous metal processing oil, particularly aluminum or It is very excellent as a processing oil for aluminum alloys.

  Furthermore, the metalworking oil composition of the present invention can be used as a lubricant other than machined parts of machine tools, such as a sliding surface oil, a bearing oil, and a hydraulic equipment oil. This is very useful in that the machine can save space and energy.

  The sliding surface oil referred to in the present invention refers to a lubricating oil used in a sliding mechanism guide mechanism for two abutting surfaces among constituent members of a machine tool used for cutting and grinding. For example, in a machine tool in which a workpiece is arranged on a table movable on a bed and the table is moved to convey the workpiece to a cutting / grinding tool, The sliding surface is lubricated by the sliding surface oil. In a machine tool in which a cutting / grinding tool is fixed on a bed movable on the bed, and the tool is moved toward the workpiece by moving the table, a slide between the bed and the bed is used. The moving surface is lubricated by the sliding surface oil.

  Such sliding surface oil is required to have friction characteristics such as a low friction coefficient on the sliding surface and high stick-slip prevention. When a stick-slip occurs on a sliding surface such as a machining table of a machine tool, the frictional vibration is directly transferred to the workpiece, resulting in a decrease in machining accuracy or a decrease in tool life due to the vibration. Occurs. Although the metal composition of the present invention can sufficiently prevent these phenomena when used as a sliding surface oil, it is preferable to further contain a phosphorus compound from the viewpoint of friction characteristics. .

  In addition, there are lubricating methods such as oil bearing lubrication and mist bearing lubrication for the lubrication of the bearing portion, and the oil composition of the present invention can be used for both.

  Lubricant bearing lubrication means a lubrication system in which lubricating oil is supplied to the bearing portion in a liquid state to smoothly slide the portion, and cooling of the bearing portion with the lubricating oil can be expected. As such a lubricant for bearing lubrication, since it is used at a higher temperature part, it is required that heat deterioration hardly occurs, that is, excellent heat resistance. It can also be used for such lubricant bearing lubrication.

  Mist bearing lubrication means a lubrication system in which lubricating oil is atomized by a mist generator, and the atomized oil is supplied to the bearing part with the expectation of air or the like to smoothly slide the part. Since a cooling effect by air or the like can be expected in a high-temperature part such as a part, recent machine tools often employ this lubrication method. Such a lubricant for mist lubrication is required to be resistant to thermal deterioration because it is used at a higher temperature, that is, excellent in heat resistance. It can also be used for lubricating mist bearings.

  The hydraulic equipment performs machine operation and control by hydraulic pressure, and hydraulic hydraulic oil that is expected to have a lubricating, sealing, and cooling effect is used in the hydraulic control section that controls the operation of the machinery. Since hydraulic oil is compressed to a high pressure with a pump to generate hydraulic pressure and move equipment, the lubricating oil requires high lubricity, high oxidation stability, and thermal stability. The thing can also be used for such hydraulic fluid. When the metalworking oil composition of the present invention is used as a hydraulic fluid oil, it is preferable to further contain a phosphorus compound in order to further improve the lubricity.

  Here, an example of the cutting and grinding method using the metalworking oil composition of the present invention will be described.

  FIG. 1 is an explanatory view showing an example of a machine tool that is suitably used in a cutting / grinding method with an extremely small amount of oil supply. The machine tool shown in FIG. 1 includes a table 2 that can move on the bed 1 in the direction of the arrow, and a tool 11 that is supported by the support means 10 and that can rotate in the direction of the arrow. The oil supply tank 12 contains the oil agent of the present invention, and when the workpiece 3 disposed on the table 2 is cut and ground, along with the compressed air sent from the compressed air introduction section 18, A mist-like oil of the present invention is supplied from the processing oil supply unit 13 toward the processing site. The oil agent of the present invention accommodated in the oil supply tank 12 is supplied from the sliding surface oil supply unit 14 to the sliding surface 16 between the bed 1 and the table 2 and from the bearing oil supply unit 15. It is supplied to the bearing portion between the support means 10 and the tool 11 to lubricate the sliding surface 16 and the bearing portion 17.

  As described above, in the cutting / grinding processing method of the present invention, an oil containing the same ester is used to lubricate a cutting / grinding part, a sliding surface of a machine tool, or further a bearing part. By doing so, it is possible to improve workability and work efficiency in ultra-trace oil supply type cutting / grinding.

  Further, in the cutting / grinding processing method of the present invention, as shown in FIG. 1, when the same oil is used as the oil for cutting and grinding, the oil for sliding surface, or the oil for bearings, respectively. This is preferable because it is not necessary to separately provide an oil tank or the like for supplying each oil agent, and it is possible to achieve space saving and energy saving of the machine tool.

  Although not shown in FIG. 1, in the present invention, the oil agent of the present invention stored in the oil supply tank 12 is supplied to the hydraulic equipment provided in the machine tool, and the oil agent of the present invention is used as the hydraulic fluid. You can also

The above-described hydrocarbon oil (B) of the present invention is useful as a base oil for metalworking oil, but can also be used for other applications. Other applications include rust prevention oil, cleaning agents, various ink and paint solvents, cleaning solvents, aerosol solvents, preservatives, insecticides, agricultural chemical solvents, pressure sensitive paper solvents, and surfactants. Diluent for wax, diluent for wax, cleaner, polish, automotive undercoat agent, solvent for dyeing, organosol, pigment dispersant, blanket cleaner, semiconductor cleaner, pretreatment agent for plating, various lubricants, tire manufacturing, Adhesives, mold release agents, polyolefin reaction solvents, household cleaners, NAD paints, ore flotation, printing ink cleaning fluids, car temporary protective paint (based on wax) removers, wood preservatives, herbicides, Non-carbon paper, water treatment agents, diluents for metal extraction, CO ₂ production for greenhouses, metal deep scratch agents and the like. The metal processing oil of the present invention has characteristics such that it has less odor, can improve the working environment, and has less adverse effects on rubber or plastic parts around the place where it is used.

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.
In the examples and comparative examples, the base oils and additives shown in Table 2 shown below were used. Base oils a, b, c, and d are shown below, and Table 1 shows base oils e, f, and g. Table 4 shows the fatty acid composition and total degree of unsaturation of the base oil d.

The present invention will be further described below with reference to examples and comparative examples.
(Production of hydrorefined oil of FT synthetic oil, wax hydrocracked oil, and diluent oils 1 to 3)
1) FT synthetic hydrocarbon oil made from natural gas as raw material (content of hydrocarbons with a boiling point of 150 ° C or higher: 82% by mass, content of hydrocarbons with a boiling point of 360 ° C or higher: 41% by mass) in a distillation column It was separated into a light fraction having a temperature of 150 ° C. or lower, an intermediate fraction having a boiling point of 150 to 360 ° C., and a heavy wax residue (FT wax: corresponding to a fraction having a boiling point of 360 ° C. or higher).
2) The middle distillate separated in 1) above was converted into a hydrorefining catalyst (Pt: 0.8% by mass with respect to the support, USY zeolite / silica alumina / alumina binder: weight ratio 3/57/40), hydrogen Under a stream of air, the hydrorefining treatment was performed at a reaction temperature of 311 ° C., a hydrogen pressure of 3.0 MPa, LHSV: 2.0 h ⁻¹ , and a hydrogen / oil ratio of 340 NL / L.
3) The hydrorefined oil obtained in 2) above was distilled into a 150-250 ° C. fraction (kerosene fraction 1) and a 250-360 ° C. fraction (light oil fraction 1) by distillation.
4) Using the FT wax obtained in 1) above using a hydrocracking catalyst (Pt: 0.8% by mass with respect to the support, USY zeolite / silica alumina / alumina binder: weight ratio 3/57/40) Hydrocracking was performed under a hydrogen stream at a reaction temperature of 326 ° C., a hydrogen pressure of 4.0 MPa, LHSV: 2.0 h ⁻¹ , and a hydrogen / oil ratio of 680 NL / L.
5) The hydrocracked oil obtained in 4) above was fractionated into a 150-250 ° C. fraction (kerosene fraction 2) and a 250-360 ° C. fraction (light oil fraction 2) by distillation.
Application base oil e: Gas oil fractions 1 and 2 were mixed at 56:44 (mass ratio) to obtain application base oil e.
Application base oil f: Kerosene fractions 1 and 2 were mixed at 63:37 (mass ratio) to obtain application base oil f.
Application base oil g: Polyalphaolefin (PAO)
Application base oil h: White oil Application base oil i: Gas oil fractions 1 and 2 were mixed at 51:49 (mass ratio) to obtain application base oil i.
Application base oil j: Kerosene fractions 1 and 2 were mixed at 49:51 (mass ratio) to obtain application base oil j.
And the metalworking oil composition which has a composition shown in Table 2 using these base oils was prepared, and it was tested.

(Base oil)
a: Triester of trimethylolpropane and oleic acid (kinematic viscosity at 40 ° C .: 46 mm ² / s)
b: Diester of neopentyl glycol and oleic acid (kinematic viscosity at 40 ° C .: 24 mm ² / s)
c: Diester of isodecyl alcohol and adipic acid (kinematic viscosity at 40 ° C .: 14 mm ² / s)
d: High oleic rapeseed oil (kinematic viscosity at 40 ° C .: 39 mm ² / s)
The additives used are as follows.
(Additive)
A: oleyl alcohol B: oleylamine C: oleic acid D: glycerol monooleate E: tricresyl phosphate F: sulfurized ester.

Next, the following evaluation tests were performed on each metalworking oil composition of Examples and Comparative Examples.
(Tapping test)
A tapping test was performed by a very small amount of oil supply system (MQL) or a normal oil supply system.

  In the case of the test by MQL, each metalworking oil composition and a comparative standard oil (DIDA: diisodecyl adipate) were alternately used to perform a tapping test under the following conditions, and the tapping energy was measured.

Tapping conditions (ultra-trace oil supply system (MQL))
Tool: Nut tap M8 (P = 1.25mm)
Pilot hole diameter: Φ7.2mm
Workpiece: AC8A (t = 10mm)
Cutting speed: 9.0 m / minute oil supply system Metalworking oil composition: Sprayed under conditions of compressed air 0.2 MPa, oil composition 25 ml / h DIDA: 4.3 mL / directly on the processing site without using compressed air Spraying tapping energy efficiency (min) = (tapping energy when DIDA is used) / (tapping energy when using oil composition)
Moreover, in the case of the test by a normal oil supply system, each metalworking oil composition and the comparison standard oil (DIDA: diisodecyl adipate) were used alternately, the tapping test was performed on the conditions shown below, and the tapping energy was measured. .

Tapping conditions (normal lubrication method)
Tool: Nut tap M8 (P = 1.25mm)
Pilot hole diameter: φ7.2mm
Workpiece: AC8A (t = 10mm)
Cutting speed: 9.0 m / minute oil supply system Metalworking oil composition and DIDA: Without using compressed air, spray directly onto the processing site at 4.3 mL / min.
Next, tapping energy efficiency (%) was calculated according to the following formula using the obtained tapping energy measurement value for each of the MQL and the normal fueling system.
The obtained results are shown in Tables 2 and 3. In Tables 2 and 3, the higher the tapping energy efficiency value, the higher the lubricity.
Tapping energy efficiency (%) = (Tapping energy when DIDA is used) / (Tapping energy when oil composition is used)

It is explanatory drawing which shows an example of the machine tool used suitably in the trace amount oil agent supply type cutting and grinding method.

Explanation of symbols

1 bed, 2 table, 3 workpiece, 11 tool, 12 oil supply tank, 13 processing oil supply unit, 14 sliding surface oil supply unit, 15 bearing oil supply unit, 16 sliding surface, 17 bearing unit, 18 Compressed air introduction part.

Claims (1)

20 to 95% by mass of ester oil based on the total amount of the composition ,
A kerosene oil fraction produced by a production process having at least one process selected from a Fischer-Tropsch (FT) synthesis process, a hydrocracking process of wax-containing components, and a hydrorefining process of components obtained from these processes. Yes,
Carbonization having a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 10 to 90% by mass , an aromatic content of 0 to 3% by volume , and a naphthene content of 0 to 20% by volume. A metal processing oil composition comprising 5 to 70% by mass of hydrogen oil based on the total amount of the composition.

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