JP5102965B2 - Metalworking oil composition - Google Patents

Description

  The present invention relates to a metal processing oil used in various processing of various metals.

Aluminum fins used in heat exchangers of refrigerator / freezer systems such as refrigerators and air conditioners are manufactured by plastic processing such as overhanging, drawing, punching, curling, ironing, etc. . The processing of these aluminum fin materials is usually performed using a processing oil, and a synthetic hydrocarbon such as mineral oil or isoparaffin (for example, see Patent Document 1), fatty acid, fatty acid ester, higher alcohol, α-olefin. Processing oils to which oily agents such as these are added are used. However, with these processing fluids, sufficient lubricity cannot be obtained, and aluminum may adhere to the punch or damage to the material surface may be observed. Increasing the amount of additive to solve these problems will increase the odor and worsen the working environment, incomplete removal of the oil by heat, causing discoloration and other appearance problems, water leakage It also hinders the performance of fins such as sex.
In rolling aluminum and its alloys, higher alcohols, fatty acid esters, fatty acids, alkylene glycol esterified products, α-olefins and the like have been conventionally used as oiling agents for rolling oils. Higher alcohols and then fatty acid esters are generally used. Have been used (see Patent Document 2 and Patent Document 3).

However, in order to improve productivity, it is necessary to roll the metal at a higher speed and at a higher reduction rate, and the lubrication site is exposed to a higher temperature. In addition, the rolling of high-purity materials that are generally called nine nine, three nine, and four nines with a purity of 99%, 99.9%, and 99.99% causes significant adhesion, and the lubricity is hindered. A large amount of wear powder is generated, which hinders productivity improvement.
For this reason, a sufficient rolling limit cannot be obtained by adding a conventionally known oily agent, and measures such as increasing the amount of the oily agent added or reducing the rolling speed or reduction rate are taken. However, by increasing the oiliness agent, stain generation during annealing, slippage of work rolls and rolled material, occurrence of uneven gloss on the surface of the plate after rolling, increase in the amount of wear powder, etc. Problems such as deterioration of the working environment due to the increase and an increase in rolling oil cost arise. On the other hand, lowering the rolling speed or rolling reduction is not preferable because productivity is lowered.
Japanese Patent Laid-Open No. 2-133495 No. 2003-165993 2003-165994

  The present invention has been made in view of such circumstances, and its purpose is to withstand high productivity and high workability even under severe lubrication conditions, while suppressing deterioration of work environment and product quality. An object of the present invention is to provide a metalworking oil composition that does not cause an increase in oil agent cost.

As a result of intensive studies to solve the above problems, the present inventors have improved workability in aluminum fin press and aluminum rolling by using a base oil having specific properties, and further improved the work environment. It was also found that unpleasant odor of the oil agent can be reduced.
That is, the first of the present invention is a production process having 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. A kerosene fraction produced at a temperature of 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 hydrocarbon oil naphthene content is 0 to 20 volume% of a base oil, containing a monovalent alcohol as an oily agent, further optionally oily agent, containing ester, at least one selected from carboxylic acid, The present invention relates to a metalworking oil composition containing 0.01 to 15% by mass of the oily agent containing the monohydric alcohol based on the total amount of the composition .

A hydrocarbon oil having a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 10 to 90%, an aromatic content of 0 to 3%, and a naphthene content of 0 to 20%. By using the contained metal working oil, it becomes possible to improve the workability in aluminum fin press and aluminum rolling, and to reduce the odor of the oil which is undesirable in the working environment.

Properties of hydrocarbon oil as base oil The base oil of the metalworking oil of the present invention has a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 10 to 90%, and aromatic. It contains a hydrocarbon oil having a content of 0 to 3% and a naphthene content of 0 to 20% (hereinafter referred to as “hydrocarbon oil of the present invention”).
The density (g / cm ³ , JISK2249) at 15 ° C. of the hydrocarbon oil of the present invention is 0.70 to 0.80, preferably 0.72 to 0.79, more preferably 0.73 to 0.785. is there. If the density is lower than this range, the processability is inferior. On the other hand, if it exceeds this range, the removability of the oil agent is inferior.
The n-paraffin content (% by mass) of the hydrocarbon oil of the present invention is 10-90% by mass, preferably 20-80% by mass, and more preferably 30-70% by mass. If it is less than this range, the processability is inferior, and if it is more, the solubility of the additive is inferior.
The content (volume%) of the aromatic component of the hydrocarbon oil of the present invention is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%. If the aromatic content is high, it may cause odor and skin irritation and may lead to deterioration of the working environment.
The naphthene content (volume%) of the hydrocarbon oil of the present invention is 0-20%, preferably 0-10%, more preferably 0-5%. If the naphthene content is high, an odor is emitted, which leads to deterioration of the working environment and also causes skin irritation.
The kinematic viscosity (mm ² / s, JISK2283) at 40 ° C. of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0.5-9, more preferably 1.0-5.5, more preferably 1. 2-5.0. If the kinematic viscosity is lower than this, the processability may be inferior. On the other hand, if it exceeds this range, the removability of the oil may be inferior.

The flash point (° C.) of the hydrocarbon oil of the present invention is measured by a tag-sealed type or a penscratic tenth-type flash point test method in accordance with JIS K2265, and is not particularly limited, but is preferably 50-200. Preferably it is 55-150, More preferably, it is 58-140. A low flash point may increase the risk of fire, while a high flash point may result in poor removability.
The aniline point (° C., JIS K2256) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 65-110, more preferably 70-110, still more preferably 75-110.
The sulfur content (mass ppm, JIS K 2541) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0-30, more preferably 0-10, still more preferably 0-5, and most preferably 0-1. It is. When there is much sulfur content, odor may get worse.

Distillation properties (° C.) of the hydrocarbon oil of the present invention are as follows according to Engler distillation (JIS K2254).
The initial boiling point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 140 to 280, more preferably 150 to 275, still more preferably 160 to 270, and most preferably 165 to 265. . If it is low, the amount of oil used may increase.

The 10% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 150-290, more preferably 160-285, still more preferably 170-280, and most preferably 180-275. .
The 50% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 170-320, more preferably 180-310, still more preferably 190-300, and particularly preferably 195-290. It is.
The 90% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 180-390, more preferably 190-370, still more preferably 200-340, particularly preferably 210-330. is there.
The end point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 190 to 400, more preferably 200 to 380, still more preferably 210 to 350, and most preferably 220 to 340. If the end point (° C.) is high, the removability may be inferior.

The T ₉₀ -T ₁₀ (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 15-160, more preferably 20-150, still more preferably 30-140, and particularly preferably 35-135. When T ₉₀ -T ₁₀ (° C.) is narrow, the solubility of the additive is inferior. On the other hand, when it is wide, the property of the base oil changes greatly during rolling and the removability is inferior. .
The EP-IBP (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 35 to 200, more preferably 40 to 190, still more preferably 50 to 180, and particularly preferably 60 to 170. If EP-IBP (° C.) is narrow, the solubility of the additive is inferior. On the other hand, if the EP-IBP (° C.) is wide, the property of the base oil changes greatly during rolling and the removability is inferior.

The paraffin content (% by volume) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 80-100%, more preferably 90-100%, still more preferably 95-100%, and most preferably 99-100. %.
The saturated hydrocarbon content (volume%) of the present invention is not particularly limited, but is preferably 90-100%, more preferably 97-100%, still more preferably 98-100%, and most preferably 99-100%. It is. If the aromatic content is high, it may cause odor and skin irritation and may lead to deterioration of the working environment.
Although content (volume%) of the unsaturated part of the hydrocarbon oil of this invention is not specifically limited, Preferably it is 0-5%, More preferably, it is 0-3%, More preferably, it is 0-1%.
The cetane number (JIS K2280) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 90-100, more preferably 97-100, still more preferably 98-100, and most preferably 99-100.
The smoke point (mm, JISK2537) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0-5, more preferably 0-3, and still more preferably 0-1.

In addition, n-paraffin content here means the value (dilution oil whole quantity reference | standard) measured using GC-FID. Here, 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, a column length of 30 m, a carrier gas flow rate of 1 0.0 mL / 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 n-paraffin content (based on the total amount of diluted oil) identified and quantified by using is shown, but it is not limited to this measurement condition as long as an equivalent result is obtained.
Furthermore, the saturated content, the unsaturated content and the aromatic content 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 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”. 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 aspects and 2nd aspects are mentioned as a more concrete preferable aspect according to the use etc.
In the first aspect, the kinematic viscosity (mm ² / s) at 40 ° C. is 1.4-2.7. If the kinematic viscosity is lower than this, the workability may be inferior, whereas if it exceeds this range, the surface gloss may be inferior.
In the first embodiment, the initial boiling point (° C.) is preferably 140-260, preferably 150-255, more preferably 160-250, and most preferably 165-245. If the initial boiling point is low, the amount of oil used may increase.
In the first embodiment, the 10% distillation point (° C.) is preferably 150-270, preferably 160-265, more preferably 170-260, and most preferably 180-255.
In the first embodiment, the 90% distillation point (° C.) is preferably 180-320, preferably 190-310, more preferably 200-300, and most preferably 210-290.
In the first embodiment, the end point (° C.) is preferably 190-320, preferably 200-300, more preferably 210-290, and most preferably 220-280. If the end point (° C.) is high, the removability may be inferior.
In the second embodiment, the kinematic viscosity (mm2 / s) at 40 ° C. is 3.8-5.0.
If the kinematic viscosity is lower than this, the rolling limit at the time of rolling may be inferior. On the other hand, if it exceeds this range, the oil agent may be poorly removed.
In the second embodiment, the initial boiling point (° C.) is preferably 200-280, preferably 210-275, more preferably 220-270, and most preferably 230-265. If the initial boiling point is low, the rolling limit during strip rolling may be inferior.
In the second embodiment, the 10% distillation point (° C.) is preferably 210-290, preferably 220-285, more preferably 230-280, and most preferably 240-275.
In the second embodiment, the 90% distillation point (° C.) is preferably 220-390, preferably 230-370, more preferably 240-340, and most preferably 250-330.
In the second embodiment, the end point (° C.) is preferably 230-400, preferably 240-380, more preferably 250-350, and most preferably 260-350. If the end point (° C.) is high, the washability during strip rolling may be poor.

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. In the present invention, within this boiling range, it can be adjusted to the desired boiling range by distillation or the like, as described above for the components (A1) to (A3).

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. Preferably, it is 300 to 400 degreeC, and it is still more preferable. 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.

Examples of metals to which the metal working oil of the present invention is applied include transition metals such as copper, iron, chromium, nickel, zinc, tin, titanium, and alloys thereof, in addition to aluminum, magnesium, and alloys thereof. . Examples of applicable processing methods include metal processing such as cold, warm and hot rolling, pressing, punching, ironing, drawing, drawing, forging, and the like. In particular, press working of aluminum fin material (flat pure aluminum (purity 99% or more) or an alloy containing aluminum as a main component), high-purity aluminum (purity 99.9% or more (having a purity of 99.99% or more) Suitable for cold, warm and hot rolling of alloys containing aluminum as a main component, or metals other than aluminum and alloys containing them as a main component. In the present invention, unless otherwise specified, hereinafter, aluminum represents a generic name of pure aluminum (including high-purity aluminum) and alloys containing aluminum as a main component.
When the metal working oil of the present invention is used for press working of an aluminum fin material, the hydrocarbon oil of the first aspect is preferably used as the hydrocarbon oil of the present invention. Moreover, when using for the cold of aluminum, warm, and hot rolling, it is preferable to use the thing of the said 1st aspect or the 2nd aspect as hydrocarbon oil of this invention.

  The present invention contains the hydrocarbon oil of the present invention as an essential component of the base oil, but besides this, any of mineral oil, synthetic oil and oil can be used together, and there is no limitation on the type, For combined use, mineral oil or synthetic oil is particularly preferred. The combination ratio is not particularly limited and can be arbitrarily selected as long as the effects of the present invention are not impaired. However, the content of the hydrocarbon oil of the present invention is 10% by mass or more based on the total amount of the metal processing oil composition. It is preferably 20% by mass or more, and most preferably 30% by mass or more. Further, the content of the base oil other than the hydrocarbon oil of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass based on the total amount of the metal processing oil composition. Most preferably:

Examples of mineral oils that can be used in combination include kerosene fraction obtained by distillation of paraffinic or naphthenic crude oil; normal paraffin obtained by extraction operation from kerosene fraction; and distillation of paraffinic or naphthenic crude oil. The lubricating oil fraction obtained by the above is purified by combining one or more refining treatments such as solvent deburring, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. And the like. In addition, synthetic oils, fats and oils, and the like can be further mixed with the base oil.
Examples of synthetic oils that can be used in combination include olefin oligomers (propylene oligomers, isobutylene oligomers, polybutenes, 1-octene oligomers, 1-decene oligomers, ethylene-propylene oligomers, etc.) or their hydrides, alkylbenzenes, alkylnaphthalenes, diesters ( Ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc., polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexa) Noate, pentaerythritol pelargonate, etc.), polyglycol, silicone oil, dialkyl diphenyl ether, and poly Phenyl ether, and the like. Among these, propylene oligomer hydride, isobutylene oligomer hydride and polybutene hydride are collectively called isoparaffin.

  Examples of the fats and oils that can be used in the present invention include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, hydrogenated products thereof, or a mixture of two or more of these. It is done.

Various oil agents can be mix | blended with the metalworking oil of this invention.
Examples of such an oil agent include an epoxy compound, and examples of the epoxy compound include epoxy compounds represented by the following (E-1) to (E-8).
(E-1) Phenyl glycidyl ether type epoxy compound (E-2) Alkyl glycidyl ether type epoxy compound (E-3) Glycidyl ester type epoxy compound (E-4) Aryl oxirane compound (E-5) Alkyl oxirane compound (E -6) Alicyclic epoxy compound (E-7) Epoxidized fatty acid monoester (E-8) Epoxidized vegetable oil

Below, (E-1)-(E-8) component is explained in full detail.
Specific examples of the (E-1) phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. Examples of the alkylphenyl glycidyl ether herein include those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl. Glycidyl ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decyl Phenyl glycidyl ether etc. can be illustrated as a preferable thing.

  (E-2) Specifically, as the alkyl glycidyl ether type epoxy compound, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl Glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, poly Alkylene glycol monoglycidyl ether, polyalkylene glycol diglycy Ether and the like.

Specific examples of the (E-3) glycidyl ester type epoxy compound include compounds represented by the following general formula (1).

In said formula (1), R represents a C1-C18 hydrocarbon group. Examples of such a hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 18 carbon atoms, and a carbon number. A 6-10 aryl group, a C7-18 alkylaryl group, a C7-18 arylalkyl group, etc. are mentioned. Among these, an alkylphenyl group having an alkyl group having 5 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkyl group having 1 to 4 carbon atoms is preferable.
Specific examples of glycidyl ester type epoxy compounds include glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl-t-butyl benzoate, glycidyl acrylate, and glycidyl methacrylate.

  Specific examples of the (E-4) aryloxirane compound include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene, and the like.

  Specific examples of (E-5) alkyloxirane compounds include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, and 1,2-epoxyoctane. 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane, 1,2-epoxyicosane and the like.

(E-6) As an alicyclic epoxy compound, the compound in which the carbon atom which comprises an epoxy group directly comprises the alicyclic ring like the compound represented by following General formula (2) is mentioned. .

  Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

  Specific examples of the (E-7) epoxidized fatty acid monoester include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.

  Specific examples of (E-8) epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.

In the lubricating oil composition for metal working of the present invention, only one type of epoxy compound selected from the above (E-1) to (E-8) may be used, or two or more types may be used in combination. May be.
Moreover, in this invention, as an epoxy compound, (E-2), (E-3), and (E-5) are preferable among (E-1)-(E-8), (E-2) (E-5) is more preferable, and (E-5) is most preferable.

In the metalworking oil of the present invention, the content of the epoxy compound is 0.01 to 10.0% by mass, preferably 0.05 to 7.5% by mass, more preferably 0.1 to 6.0% based on the total amount of the composition. % By mass. If the content is less than 0.01% by mass, the lubricity improvement effect may not be expected. If the content is more than 10% by mass, not only the lubricity improvement effect corresponding to the addition amount cannot be expected, but also the removal of oil by heat is not possible. Further, in the case of rolling oil, lubricity may be hindered or gloss unevenness may occur depending on conditions.
Epoxy compounds can be used as an alternative to oily agents, and when used in combination with oily agents, the amount of oily agent used can be reduced, leading to improvements in the work environment such as odor reduction.

The metal working oil of the present invention can further contain an oxygen-containing compound in order to further improve workability. Examples of such oxygen-containing compounds include at least one oxygen-containing compound selected from the group consisting of the following components (A1) to (A8).
(A1) Alkylene oxide adduct of polyhydric alcohol having 3 to 6 hydroxyl groups having a number average molecular weight of 100 or more and 1000 or less (A2) Hydrocarbyl ether or hydrocarbyl ester of component (A1) (A3) Number average molecular weight (A4) Hydrocarbyl ether or hydrocarbyl ester of component (A3) (A5) Dihydric alcohol having 2 to 20 carbon atoms (A6) Hydrocarbyl ether of component (A5) or Hydrocarbyl ester (A7) Trivalent alcohol having 3 to 20 carbon atoms (A8) Hydrocarbyl ether or hydrocarbyl ester of component (A7) above

(A1) The polyhydric alcohol which comprises a component has 3-6 hydroxyl groups. In addition to the following polyhydric alcohols, saccharides can also be used as the polyhydric alcohol having 3 to 6 hydroxyl groups.
Examples of the polyhydric alcohol include glycerin, polyglycerin (a dimer to tetramer of glycerin, such as diglycerin, triglycerin, and tetraglycerin), trimethylol alkane (for example, trimethylolethane, trimethylolpropane, and trimethylolbutane), And 2- to 4-mer thereof, 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 and the like.
Examples of the saccharide include xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, mannose, isomaltose, trehalose, sucrose and the like. Among these, glycerin, trimethylol alkane, and sorbitol are preferable from the viewpoint of excellent processability.

Moreover, as alkylene oxide which comprises (A1) component, C2-C6, Preferably C2-C4 alkylene oxide is used. Examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene oxide, propylene oxide, 1,2-epoxybutane (α-butylene oxide), 2,3-epoxybutane (β-butylene oxide), 1,2-epoxy-1- Examples include methylpropane, 1,2-epoxyheptane, and 1,2-epoxyhexane. Among these, ethylene oxide, propylene oxide, and butylene oxide are preferable from the viewpoint of excellent processability, and ethylene oxide and propylene oxide are more preferable.
When two or more kinds of alkylene oxide are used, there is no particular limitation on the polymerization mode of the oxyalkylene group, and random copolymerization or block copolymerization may be performed. Moreover, when adding an alkylene oxide to the polyhydric alcohol which has 3-6 hydroxyl groups, you may add to all the hydroxyl groups, and you may add to only one hydroxyl group. Among these, it is preferable to add to all hydroxyl groups from the viewpoint of excellent processability.

  Furthermore, the number average molecular weight (Mn) of the component (A1) is 100 or more and 1000 or less, preferably 100 or more and 800 or less. When Mn is less than 100, the solubility in mineral oil may be reduced. On the other hand, when Mn is larger than 1000, the oil agent may remain on the surface of the processed material after the processing in the oil agent removing step. In addition, Mn in this invention says the number average molecular weight of conversion of the standard polystyrene by gel permeation chromatography (GPC).

  As (A1) component, you may use what added the alkylene oxide to the polyhydric alcohol which has 3-6 hydroxyl groups so that Mn may be 100-1000. In addition, a mixture of polyhydric alcohol alkylene oxide adducts having 3 to 6 hydroxyl groups obtained by an arbitrary method or a commercially available mixture of polyhydric alcohol alkylene oxide adducts having 3 to 6 hydroxyl groups is distilled. Alternatively, those separated so that Mn may be 100 or more and 1000 or less by chromatography may be used. In addition, as (A1) component, you may use these compounds individually or in mixture of 2 or more types.

Component (A2) is a hydrocarbyl etherified or esterified polyhydric alcohol alkylene oxide adduct having 3 to 6 hydroxyl groups with Mn of 100 or more and 1000 or less, preferably 100 or more and 800 or less. .
As the component (A2), a product obtained by hydrocarbyl etherifying or esterifying part or all of the terminal hydroxyl groups of the alkylene oxide adduct of the component (A1) can be used. The hydrocarbyl group referred to herein 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, t-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 Branch Cosyl group, straight or branched tricosyl group, tetracosyl group of straight or branched may be mentioned.

  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 Group, straight or branched tricosenyl group, tetracosenyl group of straight or branched may be mentioned.

  Examples of the cycloalkyl group having 5 to 7 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a 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 Groups (including all structural isomers), linear or branched hexylphenyl groups (including all structural isomers), linear or branched heptylphenyl groups (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) .), Including straight-chain or branched undecylphenyl (all structural isomers.), Including straight-chain or branched dodecylphenyl group (all structural isomers.), 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, from the viewpoint of excellent processability, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and a carbon number of 3 to 12 is preferable. A linear or branched alkyl group or an oleyl group (residue obtained by removing a hydroxyl group from oleyl alcohol) is more preferred.

  As the acid used for esterification, carboxylic acid is usually mentioned. The carboxylic acid may be a monobasic acid or a polybasic acid, but a monobasic acid is usually used. Examples of monobasic acids include fatty acids having 6 to 24 carbon atoms, which may be linear or branched. The monobasic acid may be a saturated fatty acid, an unsaturated fatty acid, or a mixture thereof.

  Saturated fatty acids include linear or branched hexanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, Linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched Octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched eicosanoic acid, linear or branched heneicosanoic acid, linear or branched docosanoic acid, Examples thereof include linear or branched tricosanoic acid, linear or branched tetracosanoic acid, and the like.

  Examples of unsaturated fatty acids include linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenic 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 Branched hexadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecenoic acid, linear or branched eicosenoic acid, linear or branched heneicosene Examples thereof include acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, and linear or branched tetracosenoic acid.

  Of these, saturated fatty acids having 8 to 20 carbon atoms, unsaturated fatty acids having 8 to 20 carbon atoms, and mixtures thereof are particularly preferable. In addition, as (A2) component, you may use these compounds individually or in mixture of 2 or more types.

The component (A3) is a polyalkylene glycol having a Mn of 100 or more and 1000 or less, and one obtained by homopolymerizing or copolymerizing an alkylene oxide having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Examples of the alkylene oxide having 2 to 6 carbon atoms include the alkylene oxides listed in the description of the component (A1). Among these, ethylene oxide, propylene oxide, and butylene oxide are preferable from the viewpoint of excellent processability, and ethylene oxide and propylene oxide are more preferable.
In addition, when 2 or more types of alkylene oxide is used at the time of preparation of polyalkylene glycol, there is no restriction | limiting in particular in the polymerization form of an oxyalkylene group, You may carry out random copolymerization or block copolymerization.

Moreover, as (A3) component, Mn is 100 or more and 1000 or less, Preferably it is 120 or more and 700 or less. A polyalkylene glycol having an Mn of less than 100 may reduce the solubility in mineral oil. On the other hand, polyalkylene glycol with Mn greater than 1000 may cause the oil to remain on the surface of the processed material after processing in the oil agent removing step.
Furthermore, as the component (A3), a component that is reacted so that Mn is 100 or more and 1000 or less when the alkylene oxide is polymerized may be used. Moreover, you may use what isolate | separated the polyalkylene glycol mixture obtained by arbitrary methods, and the commercially available polyalkylene glycol mixture so that Mn might be set to 100 or more and 1000 or less by distillation or chromatography. In addition, as (A3) component, you may use these compounds individually or in mixture of 2 or more types.

  The component (A4) is a hydrocarbyl etherified or esterified polyalkylene glycol having a Mn of 100 to 1000, preferably 120 to 700. As the component (A4), hydrocarbyl etherified or esterified part or all of the terminal hydroxyl groups of the polyalkylene glycol of the component (A3) can be used. The hydrocarbyl group as used herein represents a hydrocarbon group having 1 to 24 carbon atoms, and specifically includes the groups listed in the description of the component (A2). Among these, from the viewpoint of excellent processability, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and a carbon number of 3 to 12 is preferable. A linear or branched alkyl group or an oleyl group (residue obtained by removing a hydroxyl group from oleyl alcohol) is more preferred.

  Further, as the component (A4), those obtained by esterifying the terminal hydroxyl group of the polyalkylene glycol of the component (A3) can also be used. As the acid used for esterification, a carboxylic acid is usually used. The carboxylic acid may be a monobasic acid or a polybasic acid, but a monobasic acid is usually used. Specific examples include those listed in the description of the component (A2). In addition, as the component (A4), these compounds may be used alone or as a mixture of two or more.

  The component (A5) is a dihydric alcohol having 2 to 20 carbon atoms, preferably 3 to 18 carbon atoms. A dihydric alcohol here means what has no ether bond in a molecule | numerator. Examples of the dihydric alcohol having 2 to 20 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, and 2-methyl-1,3. -Propanediol, 1,5-pentanediol, 1,2-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-hexanediol, 2-ethyl-2-methyl-1,3-propanediol 2-methyl-2,4-pentanediol, 1,7-heptanediol, 1,2-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3 -Propanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-nonanediol, 2- Til-2-ethyl-1,3-propanediol, 1,10-decanediol, 1,2-decanediol, 1,11-undecanediol, 1,2-undecanediol, 1,12-dodecanediol, 1, 2-dodecanediol, 1,13-tridecanediol, 1,2-tridecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,15-heptadecanediol, 1,2-heptadecanediol 1,16-hexadecanediol, 1,2-hexadecanediol, 1,17-heptadecanediol, 1,2-heptadecanediol, 1,18-octadecanediol, 1,2-octadecanediol, 1,19-nona Decanediol, 1,2-nonadecanediol, 1,20-icosadecanediol, 1, 2-Icosadecanediol etc. are mentioned.

  Among these, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2- Ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, 12-dodecanediol and the like are preferable. In addition, as (A5) component, you may use these compounds individually or in mixture of 2 or more types.

  Component (A6) is a hydrocarbyl etherified or esterified dihydric alcohol having 2 to 20 carbon atoms, preferably 3 to 18 carbon atoms (excluding those having an ether bond in the molecule). It has been made. As the component (A6), one obtained by hydrolyzing a part or all of the terminal hydroxyl groups of the dihydric alcohol of the component (A5) can be used. The hydrocarbyl group as used herein represents a hydrocarbon group having 1 to 24 carbon atoms, and specifically includes the groups listed in the description of the component (A2). Among these, from the viewpoint of excellent processability, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and a carbon number of 3 to 12 is preferable. A linear or branched alkyl group or an oleyl group (residue obtained by removing a hydroxyl group from oleyl alcohol) is more preferable.

  As the component (A6), one obtained by esterifying one or both of the terminal hydroxyl groups of the dihydric alcohol of the component (A5) can also be used. As the acid used for esterification, carboxylic acid is usually mentioned. The carboxylic acid may be a monobasic acid or a polybasic acid, but a monobasic acid is usually used. Specific examples include those listed in the description of the component (A2). Furthermore, the ester of the component (A6) may be one obtained by esterifying one of the terminal hydroxyl groups of the dihydric alcohol of the component (A5) (partial ester), or one obtained by esterifying both of the terminal hydroxyl groups (completely). Ester). In these, it is preferable that it is a partial ester from the point which is excellent in workability. In addition, as (A6) component, you may use these compounds individually or in mixture of 2 or more types.

  The component (A7) is a trivalent alcohol having 3 to 20 carbon atoms, preferably 3 to 18 carbon atoms. The trihydric alcohol here means one having no ether bond in the molecule. Examples of the trihydric alcohol having 3 to 20 carbon atoms include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5 -Hexanetriol, 1,3,4-hexanetriol, 1,3,5-hexanetriol, 1,3,6-hexanetriol, 1,4,5-hexanetriol, 1,2,7-heptanetriol, 1 , 2,8-octanetriol, 1,2,9-nonanetriol, 1,2,10-decanetriol, 1,2,11-undecantriol, 1,2, 2-dodecanetriol, 1,2,13-tridecanetriol, 1,2,14-tetradecanetriol, 1,2,15-pentadecanetriol, 1,2,16-hexadecanetriol, 1,2,17- Examples include heptadecane triol, 1,2,18-octadecane triol, 1,2,19-nonadecane triol, 1,2,20-icosan triol.

  Among these, 1,2,12-dodecanetriol, 1,2,13-tridecanetriol, 1,2,14-tetradecanetriol, 1,2,15-pentadecanetriol, , 2,16-hexadecanetriol, 1,2,17-heptadecanetriol, 1,2,18-octadecanetriol are preferred. In addition, as (A7) component, you may use these compounds individually or as a 2 or more types of mixture.

  Component (A8) is a hydrocarbyl etherified or esterified trivalent alcohol having 3 to 20 carbon atoms, preferably 3 to 18 carbon atoms (excluding those having an ether bond in the molecule). It has been made. As the component (A8), one obtained by hydrolyzing a part or all of the terminal hydroxyl groups of the trihydric alcohol of the component (A7) can be used. The hydrocarbyl group as used herein represents a hydrocarbon group having 1 to 24 carbon atoms, and specifically includes the groups listed in the description of the component (A2). Among these, from the viewpoint of excellent processability, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and a carbon number of 3 to 12 is preferable. A linear or branched alkyl group or an oleyl group (residue obtained by removing a hydroxyl group from oleyl alcohol) is more preferred.

  Moreover, as (A8) component, what esterified one or all of the terminal hydroxyl group of the trihydric alcohol of (A7) component can be used. As the acid used for esterification, carboxylic acid is usually mentioned. The carboxylic acid may be a monobasic acid or a polybasic acid, but a monobasic acid is usually used. Specific examples include those listed above for the component (A2). The ester of the component (A8) may be one obtained by esterifying one or two terminal hydroxyl groups of the trihydric alcohol of the component (A7) (partial ester), and all the terminal hydroxyl groups are esterified. (Complete ester) may be sufficient. In these, it is preferable that it is a partial ester from the point which is excellent in workability.

  As the component (A8), glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,3,5-pentane among the components (A7) Triol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1, Hydrocarbyl ethers or moieties of 2,5-hexanetriol, 1,3,4-hexanetriol, 1,3,5-hexanetriol, 1,3,6-hexanetriol and 1,4,5-hexanetriol Esters are preferred. In addition, as (A8) component, you may use these compounds individually or in mixture of 2 or more types.

  In the present invention, one oxygen-containing compound selected from the components (A1) to (A8) may be used alone, or a mixture of two or more oxygen-containing compounds having different structures may be used. Good. Among the above components (A1) to (A8), the component (A3), the component (A4), the component (A5), and the component (A8) are preferable from the viewpoint of excellent workability, and the component (A3), (A4) The component and the component (A8) are more preferable.

  Moreover, content of the oxygen-containing compound which occupies for the metal processing oil of this invention is 0.005-10.0 mass% on the basis of the whole quantity of this processing oil. That is, the content of the oxygen-containing compound is 0.005% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. On the other hand, the content of the oxygen-containing compound is 10% by mass or less, preferably 5.0% by mass or less, more preferably 2.0% by mass or less. If the content of the oxygen-containing compound is too small, the effect of improving workability may be insufficient, and even if the content is increased, an effect commensurate with the content may not be obtained.

The metalworking oil of the present invention can further contain an oily agent. As the oily agent, in order to further improve the workability, it is preferable to use at least one oily agent selected from the following components (B1) to (B3). In addition, as an oiliness agent, what is normally used as an oiliness agent of lubricating oil is also contained.
(B1) Ester (B2) Monohydric alcohol (B3) Carboxylic acid

  The ester which is the component (B1) is obtained by reacting an alcohol with a carboxylic acid. The alcohol may be a monohydric alcohol or a polyhydric alcohol. The carboxylic acid may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol, a monohydric alcohol having 1 to 24 carbon atoms is usually used. Such alcohols may be linear or branched. Examples of the monohydric alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or branched hexanol, direct Linear or branched heptanol, 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 hexadecanol, linear or branched heptadecanol, linear or branched Octadecanol, linear or branched nonadecanol, linear or branched eicosanol, linear or branched heneicosanol, linear Other branched Torikosanoru, straight or branched tetracosanol, and mixtures thereof.

As the polyhydric alcohol, a dihydric alcohol having 2 to 10 valences, preferably 2 to 6 valences is usually used. Examples of the 2- to 10-valent alcohol include ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene oxide), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 15 mer of propylene oxide), and 1,3-propane. Diol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-pentane Diol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol, glycerin, polyglycerin (diglycerin dimer to octamer, such as diglycerin, triglycerin, tetraglycerin ), Trimethylol al (For example, trimethylolethane, trimethylolpropane, trimethylolbutane) and their 2-8 mer, pentaerythritol and their 2-4 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 and the like.
In addition, saccharides such as xylose, arabitol, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, mannose, isomaltose, trehalose, sucrose can be used.

  Among these, ethylene glycol, diethylene glycol, polyethylene glycol (more preferably, 3-10 mer of ethylene oxide), propylene glycol, dipropylene glycol, polypropylene glycol (more preferably, 3-10 mer of propylene oxide), 1, 3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylol alkane (for example, trimethylol ethane, tri Methylolpropane, trimethylolbutane) and their dimers and tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6- Hexane triol, 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 more preferable. More preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and mixtures thereof.

  Moreover, as a monobasic acid which comprises an ester oily agent, the linear or branched fatty acid which has C6-C24 normally is mentioned. The monobasic acid may be a saturated fatty acid, an unsaturated fatty acid, or a mixture thereof.

  Saturated fatty acids include linear or branched hexanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid , Linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched Branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched eicosanoic acid, linear or branched heneicosanoic acid, linear or branched docosanoic acid , Linear or branched tricosanoic acid, linear or branched tetracosanoic acid and the like.

  Examples of unsaturated fatty acids include linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenic 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 Branched hexadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecenoic acid, linear or branched eicosenoic acid, linear or branched heneicosene Examples thereof include acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, and linear or branched tetracosenoic acid. Of these, saturated fatty acids having 8 to 20 carbon atoms, unsaturated fatty acids having 8 to 20 carbon atoms, and mixtures thereof are particularly preferable.

  Examples of the polybasic acid constituting the ester oil-based agent 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 a saturated dibasic acid, an unsaturated dibasic acid, or a mixture thereof.

  Saturated dibasic acids include ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear or branched Branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid, linear or branched Examples include branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid, and the like.

  Examples of unsaturated dibasic acids include linear or branched hexene diacids, linear or branched octene diacids, linear or branched nonene diacids, linear or branched decene diacids, linear Or branched undecenedioic acid, linear or branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetracenedioic acid, linear or branched heptacenedioic acid, linear Or a branched hexadecenedioic acid etc. are mentioned.

Examples of the ester oil-based agent include the following components (1b) to (7b). As the ester oily agent, an ester obtained by reacting an arbitrary alcohol with a carboxylic acid can be used as in these exemplified components, and is not particularly limited thereto.
(1b) ester of monohydric alcohol and monobasic acid (2b) ester of polyhydric alcohol and monobasic acid (3b) ester of monohydric alcohol and polybasic acid (4b) polyhydric alcohol and polybasic acid (5b) Mixed ester of monohydric alcohol and polyhydric alcohol and polybasic acid (6b) Mixed ester of polyhydric alcohol and monobasic acid and polybasic acid (7b) Monohydric alcohol And mixed esters of polyhydric alcohols with monobasic and polybasic acids

  In addition, when a polyhydric alcohol is used as the alcohol component, the ester is a complete ester in which all hydroxyl groups in the polyhydric alcohol are esterified. When a polybasic acid is used as the carboxylic acid component, the ester may be a complete ester in which all carboxyl groups in the polybasic acid are esterified, and a part of the carboxyl group is not esterified. It may be a partial ester remaining as a carboxyl group.

  As the ester oily agent, any of the above can be used, but from the viewpoint of excellent processability, (1b) an ester of a monohydric alcohol and a monobasic acid, (2b) a polyhydric alcohol and a monobasic acid, And (3b) esters of monohydric alcohols and polybasic acids are preferred. Particularly in aluminum fin processing and aluminum rolling, (1b) an ester of a monohydric alcohol and a monobasic acid and (2b) an ester of a polyhydric alcohol and a monobasic acid are more preferable. In the rolling of a metal other than aluminum, ( 1b) esters of monohydric alcohols and monobasic acids, and (2b) esters of polyhydric alcohols and monobasic acids are more preferred, (1b) esters of monohydric alcohols and monobasic acids, and (3b) monovalents The combined use of an ester of an alcohol and a polybasic acid is most preferred.

  (1b) The total carbon number of the ester of monohydric alcohol and monobasic acid used as the oiliness agent is not particularly limited, but the total carbon number of the ester is preferably 7 or more and 9 or more from the viewpoint of improving processability. More preferably, 11 or more is most preferable. Further, from the viewpoint of oil agent removability, the total carbon number of the ester is preferably 26 or less, more preferably 24 or less, and most preferably 22 or less. Although there is no restriction | limiting in particular in carbon number of the said monohydric alcohol, C1-C10 is preferable, C1-C8 is more preferable, C1-C6 is still more preferable, C1-C4 is the most preferable. . Although there is no restriction | limiting in particular in carbon number of the said monobasic acid, C8-22 is preferable, C10-20 is more preferable, C12-18 is the most preferable. It is preferable to set the total carbon number, the carbon number of the alcohol, and the carbon number of the monobasic acid as described above. The upper limit value is likely to increase the occurrence of stain and corrosion, In consideration of the point that the fluidity is lost and the handling becomes difficult and the possibility that the solubility in the base oil is reduced and the precipitation is increased. This is because the working environment deteriorates due to odor.

The form of the ester of (3b) monohydric alcohol and polybasic acid used as the oiliness agent in the present invention is not particularly limited, but may be a diester represented by the following formula (3) or an ester of trimellitic acid. preferable.
R ¹ —O—CO (CH ₂ ) _n CO—O—R ² (3)
(In Formula (3), R ¹ and R ² are the same or different groups and represent a hydrocarbon group having 3 to 10 carbon atoms, and n represents 4 to 8).

R ¹ and R ² are preferably hydrocarbon groups having 3 or more carbon atoms in the above formula (3) from the viewpoint that the effect of improving the lubricating performance may not be expected or the working environment is deteriorated by odor. . In addition, there is a greater risk of increasing the occurrence of stains and corrosion, a greater risk of losing fluidity and difficulty in handling in winter, and a greater risk of precipitation due to a decrease in solubility in base oil. Therefore, in Formula (3), R ¹ and R ² are preferably hydrocarbon groups having 10 or less carbon atoms. In addition, there is a greater risk of increasing the occurrence of stains and corrosion, a greater risk of losing fluidity and difficulty in handling in winter, and a greater risk of precipitation due to a decrease in solubility in base oil. Therefore, n is preferably 8 or less. On the other hand, n is preferably 4 or more from the viewpoint that the effect of improving the lubrication performance may not be expected or the working environment is deteriorated by odor. Among these, n = 4 and 6 are particularly preferable from the viewpoint of availability of raw materials and price.

Examples of R ¹ and R ² of the diester include an alkyl group, an alkenyl group, an alkylcycloalkyl group, an alkylphenyl group, and a phenylalkyl group, and an alkyl group is particularly preferable. The alkyl group includes a linear alkyl group or a branched alkyl group, and a linear alkyl group and a branched alkyl group may be mixed, but a branched alkyl group is preferable. Examples of R ¹ and R ² include a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched hexyl group, and a linear or branched heptyl group. A linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group, and the like. The diester represented by the formula (3) can be obtained by any method. For example, a straight-chain saturated dicarboxylic acid having 6 to 10 carbon atoms (adipic acid, pimelic acid, corkic acid, azelaic acid in this order from 6 carbon atoms) , Sebacic acid) or a derivative thereof and an alcohol having 3 to 10 carbon atoms are exemplified. The carbon number of the monohydric alcohol for esterifying trimellitic acid is not particularly limited, but there is a greater risk of increasing the occurrence of stains and corrosion, and there is a greater risk of loss of fluidity and difficulty in handling in winter. From the point that the solubility in oil decreases and the risk of precipitation increases, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and more preferably 1 to 1 carbon atoms. 4 is most preferred. The ester of trimellitic acid may be a partial ester (monoester or diester) or a complete ester (triester).

  Examples of the monohydric alcohol of the component (B2) include the compounds listed as the alcohol constituting the ester in the description of the component (B1). As the monohydric alcohol, the total carbon number of the monohydric alcohol is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more from the viewpoint of superior processability. Further, from the viewpoint of oil agent removability, the total carbon number of the monohydric alcohol is preferably 20 or less, more preferably 18 or less, and most preferably 16 or less.

  The carboxylic acid as component (B3) may be a monobasic acid or a polybasic acid. As such carboxylic acid, the compound illustrated as carboxylic acid which comprises ester in description of the said (B1) component is mentioned, for example. Among these, a monobasic acid is preferable from the viewpoint of superior processability. Moreover, from the point which is excellent in workability, 6 or more are preferable, as for the total carbon number of carboxylic acid, 8 or more are more preferable, and 10 or more are the most preferable. Further, from the viewpoint of oil agent removability, the total carbon number of the carboxylic acid is preferably 20 or less, more preferably 18 or less, and most preferably 16 or less.

  As the oily agent used in the metalworking oil of the present invention, only one kind selected from the above-mentioned various oily agents may be used alone or as a mixture of two or more, but the workability can be further improved. (1) Ester having a total carbon number of 7 to 26 obtained from monohydric alcohol and monobasic acid, (2) Monohydric alcohol having 6 to 20 carbon atoms, particularly monohydric alcohol having 9 or more carbon atoms and carbon number 8 A combination of the following monohydric alcohols, (3) a monobasic acid having 6 to 20 carbon atoms, or a mixture thereof is preferable.

The content of the oily agent of the (B1) ~ (B3) is 15 mass% 0.01 in terms of the total amount of the metal working oil of the present invention. The content of the oily agent is 0 . It is 01 mass% or more, preferably 0.05 mass% or more, more preferably 0.07 mass% or more. On the other hand, the upper limit of the content of the oily agent, from the viewpoint of oil removability, 1 5 wt% or less, good Mashiku is 10 mass% or less.

Alkylbenzene can be blended with the metalworking oil of the present invention, and particularly, a base oil with a low aromatic content, specifically an aromatic 5 vol% or less (more specifically 1 vol% or less) mineral oil or isoparaffin. When alkylbenzene is added, the effect of adding an oily agent can be further increased. Kinematic viscosity at 40 ° C. of alkylbenzenes used in the present invention ranges from 1~60mm ² / s, when the kinematic viscosity at 40 ° C. of less than ^{1 mm} 2 / s, there is a case where the effect of addition can not be expected, 40 When the kinematic viscosity at 60 ° C. exceeds 60 mm ² / s, there is a possibility of increasing the occurrence of stains and corrosion, preferably 40 mm ² / s or less, more preferably 20 mm ² / s or less.

Further, the alkyl group bonded to the benzene ring of the alkylbenzene used in the present invention may be linear or branched, and the carbon number is not particularly limited, A C1-C40 alkyl group is preferable.
Specific examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched group. A branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a 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, straight Chain or branched nonadecyl group, linear or branched icosyl Linear or branched heicosyl group, linear or branched docosyl group, linear or branched tricosyl group, linear or branched tetracosyl group, linear or branched A branched pentacosyl group, a linear or branched hexacosyl group, a linear or branched heptacosyl group, a linear or branched octacosyl group, a linear or branched nonacosyl group, Linear or branched triacontyl group, linear or branched hentriacontyl group, linear or branched dotriacontyl group, linear or branched tritriacontyl group, linear Linear or branched tetratriacontyl group, linear or branched pentatriacontyl group, linear or branched hexatriacontyl group, linear or branched heptatria Contyl group, straight chain The branched oct triacontyl group, straight or branched nonadecyl triacontyl group include linear or branched tetracontyl group.

  The number of alkyl groups in the alkylbenzene is usually 1 to 4, but from the viewpoint of stability and availability, alkylbenzene having 1 or 2 alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or a mixture thereof is used. Most preferably used. Of course, the alkylbenzene to be used may be not only a single structure alkylbenzene but also a mixture of alkylbenzenes having different structures.

  The number average molecular weight of the alkylbenzene according to the present invention is not limited at all, but is preferably 100 or more and more preferably 130 or more from the viewpoint of the effect of addition. Further, if the molecular weight is too large, the possibility of increasing the occurrence of stain or corrosion increases, so the upper limit of the number average molecular weight is preferably 340 or less, more preferably 320 or less.

  The metalworking oil of this invention can contain 0.1-50 mass% of above-mentioned alkylbenzene on the basis of the composition whole quantity. The lower limit of the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more from the viewpoint of the effect of addition. Moreover, since possibility that the generation | occurrence | production of a stain and corrosion will increase when there is too much content, upper limit is preferable 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. is there.

The metal processing oil of the present invention may further contain a linear olefin having 6 to 40 carbon atoms. When the processing oil contains a linear olefin, the lubricity is further improved.
Straight chain olefins having less than 6 carbon atoms are not suitable because of their low flash point. In order to have an appropriate flash point, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more. On the other hand, when the number of carbon atoms exceeds 40, it is difficult to use because it is in a solid state, and it is not suitable because it is difficult to mix and dissolve with other components (mineral oil and additives). Moreover, linear olefins having more than 40 carbon atoms are not common and are difficult to obtain. In view of such inconvenience, a linear olefin having 30 or less carbon atoms is preferable.

Such a linear olefin may have one double bond or two or more in the molecule, but has one double bond. What is doing is preferable. The position of the double bond is not particularly limited, but is preferably a linear olefin having a double bond at the terminal, that is, an n-α-olefin, from the viewpoint of excellent lubricity.
Examples of the linear olefin include 1-octene, 1-decene, 1-docosene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene or a mixture of two or more thereof. In addition, although what is obtained by various manufacturing methods can be used as a linear olefin, For example, the ethylene oligomer obtained by superposing | polymerizing ethylene by a normal means can be used. Moreover, as a linear olefin, you may use these compounds individually or in mixture of 2 or more types.

  In addition, although content of a linear olefin is arbitrary, from a viewpoint of the lubricity improvement of the metal processing oil of this invention, this content is preferably 1 mass% or more on the basis of the total amount of the processing oil, and is 3 mass% or more. Is more preferable, and 5 mass% or more is still more preferable. On the other hand, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less on the basis of the total amount of the processing oil from the viewpoint that an effect commensurate with the addition amount is obtained.

In the metalworking oil of the present invention, extreme pressure additives, antioxidants, rust inhibitors, corrosion inhibitors, antifoaming agents, anti-emulsifiers, antifungal agents are added as necessary in order to further improve the excellent effects. An additive such as an agent can be further contained alone or in combination of two or more.
Examples of extreme pressure additives include phosphorus compounds such as tricresyl phosphate, and organometallic compounds such as zinc dialkyldithiophosphate. Examples of the antioxidant include phenolic compounds such as 2,6-ditertiary butyl-p-cresol (DBPC), aromatic amines such as phenyl-α-naphthylamine, and organometallic compounds such as zinc dialkyldithiophosphate. Examples of rust inhibitors include salts of fatty acids such as oleic acid, sulfonates such as dinonylnaphthalene sulfonate, partial esters of polyhydric alcohols such as sorbitan monooleate, amines and derivatives thereof, phosphate esters and derivatives thereof. It is done. Examples of the corrosion inhibitor include benzotriazole. Examples of antifoaming agents include silicone-based ones. Surfactant is used as demulsifier, quaternary ammonium salt, imidazoline type as cationic system, sulfated oil, aerosol type as anionic system, ethylene oxide adduct of castor oil as nonionic system, phosphorus of ether type nonionic active agent Examples thereof include acid esters, block copolymers of ethylene oxide and propylene oxide, and esters with dimer acid. Examples of mold inhibitors include phenol compounds, formaldehyde donor compounds, salicylanilide compounds, and the like.
The total content of the additives is usually 15% by mass or less, preferably 10% by mass or less, based on the total amount of the metalworking oil of the present invention.

  In principle, the metalworking oil of the present invention (hereinafter also referred to as the composition of the present invention) should be used in a water-free state that does not substantially contain water except for the natural moisture absorption during storage. Can further contain water, and the composition of the present invention can be used in combination with water. When water is contained, the composition of the present invention comprises water in a continuous layer in which an oil component is finely dispersed to form an emulsion, a solubilized state in which water is dissolved in the oil component, or strong. Any form of a suspension in which water and an oil are mixed by stirring can be used. Further, the composition of the present invention and water can be separately supplied to the processing site for use. By simply diluting the composition (stock solution) of the present invention with water or using it together with water, it is possible to obtain a metal working oil that is actually used. The dilution ratio (when used in combination, the ratio of the stock solution + water to the stock solution is the dilution factor) is arbitrarily selected depending on the use conditions, but generally the stock solution is 2 to 100 times by weight, preferably 3 It is customary to dilute up to 70 times with water to obtain a practical metalworking oil. In this case, tap water, industrial water, ion exchange water, distilled water, etc. can be used as the dilution water, and it does not matter whether it is hard water or soft water. In the case of the emulsion type, when the composition of the present invention is diluted with water, an emulsion in which the oil component is finely dispersed in water as a continuous phase is obtained, but the average particle size of oil droplets dispersed in water is It is preferably 300 nm or less, particularly 100 nm or less. This is because if the average particle size of the dispersed oil droplets is large, oil pits are easily generated and the surface gloss of the processed product is impaired, and a fine filter cannot be used for cleaning the metalworking fluid.

The viscosity of the metal working oil of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is 0.5 to 500 mm ² / s, preferably 1.0 to ²⁰⁰ mm ² / s. In aluminum fin processing, from the viewpoint of processability, oil volatility, and oil removability, it is preferably 1.0 to 5.0 mm ² / s, more preferably 1.2 to 3.0 mm ² / s, most preferably. Is 1.3 to 2.8 mm ² / s. In the aluminum rolling, in view of lubricity and surface quality, and preferably from 1.0 to 10 mm ² / s, more preferably 1.0~8.0mm ² / s. In the rolling process of metals other than aluminum, it is preferably 1.0 to ²⁰ mm ² / s, more preferably 2.0 to 15 mm ² / s, and most preferably 3.0 to 15 mm ² / s.

  The metal processing oil of the present invention is used as a processing oil for various metals, and examples of applicable metals include aluminum, magnesium, and transition metals such as copper, iron, chromium, nickel, zinc, tin, titanium, and the like. Can be mentioned. Examples of applicable processing methods include cold, warm and hot rolling, pressing, punching, ironing, drawing, drawing, forging, metal processing such as cutting and grinding, including micro-trace cutting (MQL), etc. Can do. The lubricating oil composition for metal processing of the present invention is particularly suitable for processing aluminum fin materials (flat pure aluminum (purity 99% or more) or alloys containing aluminum as a main component), cold and warm of various metals. And suitable for cold rolling. Among these rolling methods, it is particularly suitable for cold rolling. Among various metal rolling, high purity aluminum (purity 99.9% or more (including those having a purity of 99.99% or more)) and alloys mainly composed of aluminum, stainless steel, copper and copper alloys Suitable for rolling, and most preferred is rolling of high-purity aluminum and aluminum-based alloys.

In the processing of the aluminum fin material, the metal processing oil of the present invention can be used not only for a pre-coating material in which the surface of the aluminum fin material is previously coated, but also for a material that has not been subjected to such processing.
Here, the term “film” refers to a film comprising a corrosion-resistant base film formed on an aluminum fin material and a hydrophilic film formed on the film. Examples of the corrosion resistant undercoat include inorganic undercoat and organic undercoat. Examples of the inorganic base coating include a chromate coating, a boehmite coating, a silicate coating, or a combination of these. Examples of the organic base coating include vinyl resins such as polyvinyl chloride-vinyl acetate, polyethylene, and polypropylene, acrylic resins, epoxy resins, urethane resins, styrene resins, phenol resins, and fluorine resins. And silicon resins, diallyl phthalate resins, polycarbonate resins, polyamide resins, alkyd resins, polyester resins, urea melamine resins, polyacetal resins and fiber resins.

Examples of the hydrophilic film include the following (a) to (e).
(A) a main component of a low-molecular organic compound having a carbonyl group and an alkali silicate;
(B) Special water glass mainly composed of the above (a) added with a water-soluble organic polymer compound,
(C) Sodium silicate, potassium silicate, silicate such as water glass, silicic acid, silica gel or alumina sol,
(D) a hydrophilic modified organic polymer obtained by reacting a crosslinking agent comprising a low molecular weight organic compound having a carbonyl group with a hydrophilic organic polymer;
(E) A hydrophilic polyvinyl alcohol-based modified organic polymer obtained by reacting a polyvinyl alcohol-based hydrophilic organic polymer, a water-soluble organic polymer and a crosslinking agent.
Examples of the processing of the alnium fin material include overhang processing, drawing processing, punching processing, curling processing, and ironing processing that squeezes and raises the cylindrical rising wall around the tube insertion hole.
The above-described hydrocarbon oil of the present invention is used as a base oil for metalworking oil, but can also be used for other applications. Other applications include two-cycle engine oil, rust prevention oil, cleaning agents, various ink and paint solvents, cleaning solvents, aerosol solvents, preservatives, insecticides, pesticide solvents, and pressure sensitive paper. Solvent, surfactant diluent, wax, cleaner, polish diluent, automotive undercoat agent, dyeing solvent, organosol, pigment dispersant, blanket cleaner, semiconductor cleaner, pretreatment agent for plating, various lubricants Oil, tire manufacturing, adhesives, mold release agents, polyolefin reaction solvents, household cleaners, NAD paints, ore flotation, printing ink cleaning liquids, car temporary protective paints (based on wax) removers, wood preservatives Agents, herbicides, non-carbon paper, water treatment agents, diluents for metal extraction, CO2 production for greenhouses, metal deep wound agents and the like. The hydrocarbon oil of the present invention has characteristics such that it has little odor, can improve the working environment, and has little adverse effect on rubber or plastic parts around the place where it is used.

[Example]
The following examples further illustrate the present invention.
(1) Production method of base oil (production of hydrorefined oil of FT synthetic oil, wax hydrocracked oil, and base oils 1 to 6 of the present application)
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.
Base oil 1: Light oil fractions 1 and 2 were mixed at 56:44 (mass ratio) to obtain base oil 1.
Base oil 2: Light oil fractions 1 and 2 were mixed at 51:49 (mass ratio) to obtain base oil 2.
Base oil 3: Kerosene fractions 1 and 2 were mixed at 63:37 (mass ratio) to obtain base oil 3.
Base oil 4: Kerosene fractions 1 and 2 were mixed at 49:51 (mass ratio) to obtain base oil 4.
Base oil 5: The hydrorefined oil and hydrocracked oil obtained above were mixed, and a fraction at 230 to 270 ° C. (base oil 5) was obtained by atmospheric distillation.
Base oil 6: The hydrorefined oil and hydrocracked oil obtained above were mixed, and a fraction of 250 to 305 ° C. (base oil 6) was obtained by atmospheric distillation.
(Base oil 7-10, Base oil 11-12)
Base oil 7-10: Hydrorefined mineral oil was used.
Base oil 11-12: Isoparaffin was used.

(2) Properties of base oil Tables 1 and 2 show properties of base oils 1 to 12.

In this example, a test as an aluminum rolling oil is performed.
Metal processing oils were prepared by blending the base oils in Tables 1 and 2 with butyl stearate, lauryl alcohol, and oleic acid as oiliness agents in the amounts shown in Table 3 .
Subsequently, the obtained processing oil was subjected to an aluminum rolling test, an odor determination, and an oil agent removal test.
All the results are shown in Table 3 below.

Testing method for rolling:
Using aluminum (JIS A1050, thickness 0.15 mm, width 78 mm), rolling was performed at a rolling speed of 250 m / min and a reduction rate of 35%, and the load required for processing was measured. A smaller required load is preferable because of good workability.

Odor measurement method:
The odor was determined with the sample oil heated to 40 ° C.
The panel was evaluated by 10 people, and the scoring criteria were not concerned: 0 points, somewhat odor: 2 points, 4 points with odor, and scored and averaged for each sample oil.
The result was ○ less than 1 point, △ 1 point or more and less than 2 points, and 2 or more points ×.
Oil removal test:
0.2 ml of sample oil is dropped into an aluminum cup having a diameter of 4.5 cm, the temperature is raised from room temperature to 350 ° C. over 1 hour, held for 2 hours, then cooled to room temperature, and the degree of occurrence of stain is evaluated. The thing without a stain is set as (circle) and a certain thing is set as x.
All the results are shown in Table 3 below.

In this example and the reference example , a test as an aluminum fin processing oil is performed.
Metal processing oils were prepared by blending butyl stearate, lauryl alcohol, 1-tetradecene and tetrapropylene glycol with the base oils in Tables 1 and 2 in the amounts shown in Table 4 .

Next, the obtained processing oil was tested for aluminum fin processing. That is, the coefficient of friction was evaluated as the lubricity. Odor and dryness were also evaluated.
All the results are shown in Table 4.

The test methods for the test items are as follows.
Lubricity test method:
Material Aluminum JIS A1050 material The coefficient of friction is evaluated by the Bowden test.
Load 250g, sliding speed 100mm / s,

Odor measurement method:
The odor was determined with the sample oil heated to 40 ° C.
The panel was evaluated by 10 people, and the scoring criteria were not concerned: 0 points, somewhat odor: 2 points, 4 points with odor, and scored and averaged for each sample oil.
The result was ○ less than 1 point, △ 1 point or more and less than 2 points, and 2 or more points ×.
Drying evaluation method:
The aluminum test piece washed with the solvent is allowed to stand in a constant temperature bath at 150 ° C. for 5 minutes and weighed to obtain A (g). Next, this test piece is cooled to room temperature in a desiccator, sample oil is applied at 2.5 g / m ² , and the mass of the test piece before and after application is defined as B (g) and C (g). This test piece is allowed to stand for 5 minutes in a constant temperature bath at 150 ° C., and then immediately weighed to obtain D (g). The evaporation amount of the sample oil is determined from the obtained masses by the following formula.
Evaporation (%) = 100 x (D-A) / (C-B)
All the results are shown in Table 4.

Claims (1)

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. the hydrocarbon oils as a base oil, containing a monovalent alcohol as an oily agent,
Furthermore, as an optional oily agent, it contains at least one selected from esters and carboxylic acids, and contains 0.01% by mass to 15% by mass of the oily agent containing the monohydric alcohol based on the total amount of the composition. A metalworking oil composition.