JP4865429B2 - Metalworking oil composition - Google Patents

Description

  The present invention relates to metalworking oil compositions.

  Conventionally, in the field of metal processing, metal processing oil has been used to lubricate the processing site of a metal workpiece. Such metalworking oil has a characteristic (hereinafter referred to as “workability”) that can achieve reduction in processing force, improvement in productivity, improvement in surface condition of the workpiece (for example, gloss after rolling), etc. by good lubrication. ) Is required.

Therefore, as conventional metal processing oil, in order to improve processability, oil blending agents and additives such as extreme pressure agents are generally used (for example, see Patent Documents 1 and 2). ).
JP-A-10-27385 JP 2003-165994 A

  However, recently, further improvement in machining accuracy and machining efficiency is desired, and it has become impossible to achieve sufficient workability with the conventional metal working oil.

  As a means for improving the workability of the metal working oil, a method of increasing the ratio of the fluid lubrication region having a small friction coefficient by increasing the viscosity of the metal working oil is conceivable. However, since the optimal thickness of the oil film formed by metalworking oil varies depending on the type of metalworking and processing conditions, increasing the viscosity of metalworking oil often deviates from the optimum oil film thickness. Processability cannot be achieved. In addition, increasing the viscosity of metalworking oil also has a problem that it is difficult for the oil component to be removed from the workpiece in the oil component removal step that is provided after the processing step.

  In addition, it is possible to improve the workability to some extent by increasing the amount of additives such as oiliness agents and extreme pressure agents added to the metalworking oil, but the processability improvement effect by this method is naturally limited. Therefore, it is not always easy to obtain sufficient workability. Further, even when the amount of these additives is increased, it is difficult for the oil component to be removed from the workpiece in the oil component removing step provided at the subsequent stage of the processing step. In addition, the use of a large amount of additives leads to an increase in cost and deterioration of the working environment (generation of odor, etc.). Furthermore, in addition to the harsh processing conditions, metal processing oil can maintain stable properties for a long period of time from the viewpoint of effective use of resources, reduction of waste oil, cost reduction of metal processing oil users, etc. However, an increase in the oiliness agent and extreme pressure agent also causes a decrease in the heat and oxidation stability of the metalworking oil.

  The present invention has been made in view of such circumstances, and can provide excellent processability without increasing the viscosity or increasing the amount of additives, and can be removed from the workpiece after processing. The object is to provide an excellent metalworking oil.

In order to solve the above-mentioned problems, the present invention is designed to remove a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of a crude oil, solvent extraction, solvent extraction, hydrocracking, solvent dewaxing, catalytic desorption. Select from paraffinic mineral oil, normal paraffinic base oil and isoparaffinic base oil refined by combining one or more of wax, hydrorefining, sulfuric acid washing or clay treatment alone or in combination At least one lubricant base oil, wherein % C _A is 2 or less,% C _P /% _CN is 6 or more and 35 or less , and iodine value is 2.5 or less, an ester, Provided is a metalworking oil composition comprising alcohol, carboxylic acid, and at least one lubricity improver selected from compounds containing phosphorus and / or sulfur as constituent elements.

The lubricating base oil contained in the metalworking oil composition of the present invention has excellent friction characteristics because% C _A ,% C _P /% C _N , and iodine value each satisfy the above conditions. In addition, the oil film can be sufficiently prevented from being broken by reducing the shear resistance in the fluid lubrication region. Further, the lubricating base oil is improved when at least one lubricating improver selected from esters, alcohols, carboxylic acids, and compounds containing phosphorus and / or sulfur as constituent elements is blended. The effect of improving the lubricity in the boundary lubrication region caused by the lubricity improver can be expressed at a higher level while the agent is stably dissolved and held. Furthermore, since the lubricating base oil has sufficient thermal / oxidative stability, the above-described excellent lubricating properties can be maintained for a long period of time.

  Therefore, according to the metalworking oil composition of the present invention, excellent workability can be stably obtained over a long period of time. Furthermore, in the metalworking oil composition of the present invention, it is not necessary to increase the viscosity or increase the additive in order to obtain the above-described processability and long-term maintainability. It is also excellent in terms of removability from a later work piece.

  According to the present invention, there is provided a metalworking oil composition that can obtain excellent processability without increasing the viscosity or increasing the amount of additives, and is excellent in removability from the workpiece after processing. The

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

In the present invention,% C _A of 2 or _less,% C P _/% C _N is 6 or more, the lubricating base oil having an iodine value of 2.5 or less (hereinafter, simply referred to as "lubricating base oil according to the present invention" .) Is used.

% C _A of the lubricating base oil according to the present invention is 2 or less as described above, preferably 1.5 or less, more preferably 1 or less. When% C _A of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will be lowered. Moreover,% C _A of the lubricating base oil according to the present invention may be 0% by 0.1 or more C _A, it is possible to further increase the solubility of additives.

The ratio of the lubricating base% in oil _{C P} and% _{C N} of the present invention _{(% C P /% C N} ) is at street 6 or above, and more preferably 7 or more. When% C _P /% _CN is less than the above lower limit, viscosity-temperature characteristics, thermal / oxidative stability and friction characteristics are reduced, and further, when an additive is blended in a lubricating base oil The effectiveness of the agent is reduced. _{Moreover,% C} P /% C _N is preferably 35 or less, more preferably 20 or less, further preferably 14 or less, and particularly preferably 13 or less. % Of C P _/% C _N by the above-described upper limit or less, it is possible to further increase the solubility of additives.

Further, the% C _p of the lubricating base oil according to the present invention is preferably 80 or more, more preferably 82 to 99, still more preferably 85 to 95, and particularly preferably 87 to 93. When% C _p of lubricating base oil is less than the above lower limit, viscosity-temperature characteristics, thermal / oxidative stability, and friction characteristics tend to decrease, and further, additives are added to lubricating base oil In addition, the effectiveness of the additive tends to decrease. Further, when the% C _p value of the lubricating base oil exceeds the upper limit value, the additive solubility will tend to be lower.

Moreover,% _{C N} of the lubricating base oil according to the present invention is preferably 19 or less, more preferably 5 to 15, more preferably 7 to 13, particularly preferably 8 to 12. If the% C _N value of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced. Moreover, when% _CN is less than the said lower limit, it exists in the tendency for the solubility of an additive to fall.

Incidentally, _say% C P in the present invention,% _C A _N and% _{C A,} obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number The percentage of the total number of naphthene carbons to the total number of carbons, and the percentage of the total number of aromatic carbons to the total number of carbons. That is, the preferred ranges of% C _P ,% C _N and% C _A described above are based on the values obtained by the above method. For example, even a lubricating base oil containing no naphthene is obtained by the above method. is% C _N may indicate a value greater than zero.

  In addition, the iodine value of the lubricating base oil according to the present invention is 2.5 or less as described above, preferably 1.5 or less, more preferably 1 or less, still more preferably 0.8 or less, Although it may be less than 0.01, it is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.5 or more, from the viewpoint of small effects that are commensurate with it and economy. is there. By setting the iodine value of the lubricating base oil to 2.5 or less, the thermal and oxidation stability can be dramatically improved. The “iodine value” in the present invention means an iodine value measured by an indicator titration method of JIS K 0070 “acid value, saponification value, iodine value, hydroxyl value, and unsaponification value of a chemical product”. .

The lubricating base oil according to the present invention is not particularly limited as long as% C _A ,% C _P /% C _N , and iodine value satisfy the above conditions. Specifically, a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid % C _A ,% C among paraffinic mineral oils, normal paraffinic base oils, isoparaffinic base oils, etc., which are refined by combining one or more kinds of purification treatments such as washing and clay treatment alone or in combination of two or more. Examples include _P /% C _N and iodine value satisfying the above conditions. These lubricating base oils may be used alone or in combination of two or more.

As a preferable example of the lubricating base oil according to the present invention, the following base oils (1) to (8) are used as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil is determined in advance. The base oil obtained by refine | purifying by the refining method of this, and collect | recovering lubricating oil fractions can be mentioned.
(1) Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO)
(3) Wax (such as slack wax) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-liquid (GTL) process, etc.
(4) One or two or more mixed oils selected from base oils (1) to (3) and / or mild hydrocracking treatment oils of the mixed oils (5) selected from base oils (1) to (4) 2 or more kinds of mixed oils (6) Base oil (1), (2), (3), (4) or (5) debris oil (DAO)
(7) Mild hydrocracking treatment oil (MHC) of base oil (6)
(8) Two or more mixed oils selected from base oils (1) to (7).

  The above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay purification; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable. In the present invention, one of these purification methods may be performed alone, or two or more may be combined. Moreover, when combining 2 or more types of purification methods, the order in particular is not restrict | limited, It can select suitably.

Furthermore, the lubricating base oil according to the present invention is obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment. The following base oil (9) or (10) is particularly preferred.
(9) The base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like. Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or distillation after the dewaxing treatment (10) The above base oils (1) to (8) ) Or a lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing. Hydroisomerized mineral oil obtained by performing a dewaxing process such as or by distillation after the dewaxing process.

  Moreover, when obtaining the lubricating base oil of (9) or (10) above, a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.

  The catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one of the composite oxides. Hydrogenolysis with a combination of the above combined with a binder and supporting a metal having hydrogenation ability (for example, one or more metals such as Group VIa metal or Group VIII metal in the periodic table) Hydroisomerization catalyst in which a catalyst or a support containing zeolite (for example, ZSM-5, zeolite beta, SAPO-11, etc.) is loaded with a metal having a hydrogenation ability containing at least one of Group VIII metals Are preferably used. The hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.

  The reaction conditions in the hydrocracking / hydroisomerization are not particularly limited, but the hydrogen partial pressure is 0.1 to 20 MPa, the average reaction temperature is 150 to 450 ° C., the LHSV is 0.1 to 3.0 hr-1, and the hydrogen / oil ratio. It is preferable to set it as 50-20000 scf / b.

  Preferable examples of the method for producing a lubricating base oil according to the present invention include production method A shown below.

That is, the manufacturing method A according to the present invention includes:
NH ₃ to the carrier desorption of the fraction of the NH ₃ is 80% or less at 300 to 800 ° C. relative to the total desorption of NH ₃ in the desorption temperature dependence evaluation, at least one of the periodic table Group VIa metals And a first step of preparing a hydrocracking catalyst on which at least one of the Group VIII metals is supported,
In the presence of a hydrocracking catalyst, a feed oil containing 50% by volume or more of slack wax, hydrogen partial pressure 0.1-14 MPa, average reaction temperature 230-430 ° C., LHSV 0.3-3.0 hr ⁻¹ , hydrogen oil ratio A second step of hydrocracking at 50-14000 scf / b;
A third step of obtaining a lubricating oil fraction by distilling and separating the cracked product oil obtained in the second step;
And a fourth step of dewaxing the lubricating oil fraction obtained in the third step.

  Hereinafter, the production method A will be described in detail.

(Raw oil)
In the production method A, a raw material oil containing 50% by volume or more of slack wax is used. The “raw oil containing 50% by volume or more of slack wax” as used in the present invention is a mixed oil of a raw oil consisting only of slack wax, slack wax and other raw material oil, and 50 volumes of slack wax. % And both raw material oils containing at least% are included.

Slack wax is a wax-containing component by-produced in the solvent dewaxing step when producing a lubricating base oil from a paraffinic lubricating oil fraction. In the present invention, the slack wax is obtained by further deoiling the wax-containing component. Included in wax. The main components of slack wax are n-paraffins and branched paraffins (isoparaffins) with few side chains, and are low in naphthenes and aromatics. The kinematic viscosity of the slack wax used for the preparation of the raw material oil can be appropriately selected according to the kinematic viscosity of the target lubricating base oil, but a low viscosity base oil is produced as the lubricating base oil according to the present invention. For this purpose, a relatively low viscosity slack wax having a kinematic viscosity at 100 ° C. of about ² to 25 mm ² / s, preferably about 2.5 to ²⁰ mm ² / s, more preferably about 3 to 15 mm ² / s. desirable. Moreover, although the other property of slack wax is also arbitrary, melting | fusing point becomes like this. Preferably it is 35-80 degreeC, More preferably, it is 45-70 degreeC, More preferably, it is 50-60 degreeC. The oil content of the slack wax is preferably not more than mass%, more preferably not more than 50 mass%, still more preferably not more than 25 mass%, particularly preferably not more than 10 mass%, and preferably not less than 0.5 mass%. More preferably, it is 1% by mass or more. The sulfur content of the slack wax is preferably 1% by mass or less, more preferably 0.5% by mass or less, and preferably 0.001% by mass or more.

  Here, the oil content of the fully deoiled slack wax (hereinafter referred to as “slack wax A”) is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass. The sulfur content of the slack wax A is preferably 0.001 to 0.2% by mass, more preferably 0.01 to 0.15% by mass, and still more preferably 0.05 to 0.12% by mass. On the other hand, the oil content of slack wax (hereinafter referred to as “slack wax B”) that is not deoiled or insufficiently deoiled is preferably 10 to 60% by mass, more preferably 12 to 50% by mass. More preferably, it is 15 to 25% by mass. The sulfur content of the slack wax B is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.5% by mass, and still more preferably 0.15 to 0.25% by mass. The slack waxes A and B may be subjected to a desulfurization treatment depending on the type and characteristics of the hydrocracking / isomerization catalyst, and the sulfur content in that case is preferably 0.01. It is at most mass%, more preferably at most 0.001 mass%.

In the above-described manufacturing method A, by using the slack wax A as a raw _{material,% C A,% C P} /% C N and the iodine value obtained suitably such lubricating base oil in each of the above conditions are satisfied the present invention be able to. In addition, according to the above production method A, even if slack wax B having a relatively high oil content and sulfur content, and relatively poor and inexpensive is used as a raw material, the viscosity index is high, and low temperature characteristics and thermal / oxidative stability are excellent. In addition, a lubricating base oil with high added value can be obtained.

  When the raw material oil is a mixed oil of slack wax and other raw material oil, the other raw material oil is not particularly limited as long as the ratio of slack wax to the total amount of the mixed oil is 50% by volume or more. A heavy oil-distilled distillate and / or a mixed oil of vacuum-distilled distillate is preferably used.

  Further, when the raw material oil is a mixed oil of slack wax and another raw material oil, the ratio of slack wax in the mixed oil is more preferably 70% by volume or more from the viewpoint of producing a base oil having a high viscosity index. 75% by volume or more is even more preferable. When the ratio is less than 50% by volume, the oil base such as aromatics and naphthenes in the obtained lubricating base oil tends to increase and the viscosity index of the lubricating base oil tends to decrease.

  On the other hand, the heavy atmospheric distillation distillate and / or vacuum distillation distillate of crude oil used in combination with slack wax has a distillation temperature of 300 to 570 ° C. in order to keep the viscosity index of the lubricating base oil produced high. A fraction having a distillate component of 60% by volume or more in the range is preferable.

(Hydrocracking catalyst)
In the manufacturing method A, the carrier desorption of the fraction of the NH ₃ is 80% or less at 300 to 800 ° C. relative to the total desorption of NH ₃ in the NH ₃ desorption temperature dependence evaluation, periodic table Group VIa A hydrocracking catalyst in which at least one of the metals and at least one of the Group VIII metals is supported is used.

Here, “NH ₃ desorption temperature dependency evaluation” refers to literature (Sawa M., Niwa M., Murakami Y., Zeolites 1990, 10, 532, Karge HG, Dondur V., J. Phys. Chem., 1990, 94, 765, etc.) and is performed as follows. First, the catalyst carrier is pretreated at a temperature of 400 ° C. or higher for 30 minutes or more under a nitrogen stream to remove adsorbed molecules, and then adsorbs NH ₃ at 100 ° C. until saturation. Then, the catalyst support to 100 to 800 ° C. 10 ° C. / min was heated by the following heating rate desorbed NH _3, to monitor the NH ₃ separated at every predetermined temperature by desorption. Then, the fraction of the NH ₃ desorption amount at 300 ° C. to 800 ° C. with respect to the total NH ₃ desorption amount (desorption amount at 100 to 800 ° C.) is obtained.

The catalyst carrier used in the production method A are those desorption of the fraction of NH ₃ at 300 to 800 ° C. relative to the total desorption of NH ₃ in the NH ₃ desorption temperature dependence evaluation of the following 80% , Preferably 70% or less, more preferably 60% or less. By constituting a hydrocracking catalyst using such a carrier, the acid properties that govern the cracking activity are sufficiently suppressed, so that the high molecular weight n-paraffin derived from slack wax or the like in the raw oil by hydrocracking. The production of isoparaffin by decomposition isomerization can be performed efficiently and reliably, and excessive decomposition of the produced isoparaffin compound can be sufficiently suppressed. As a result, a sufficient amount of molecules having a moderately branched chemical structure and a high viscosity index can be provided in an appropriate molecular weight range.

  As such a support, a binary oxide which is amorphous and has an acid property is preferable. For example, it is exemplified in the literature ("Metal oxide and its catalytic action", Tetsuro Shimizu, Kodansha, 1978). And binary oxides.

Among them, an amorphous composite oxide which is an acid composed of two kinds of oxides of elements selected from Al, B, Ba, Bi, Cd, Ga, La, Mg, Si, Ti, W, Y, Zn and Zr. It is preferable to contain a property binary oxide. By adjusting the ratio of each oxide of these acid property binary oxides, a support having an acid property suitable for this purpose can be obtained in the NH ₃ adsorption / desorption evaluation. In addition, the acid property binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder.

  Further, the carrier is amorphous silica / alumina, amorphous silica / zirconia, amorphous silica / magnesia, amorphous silica / titania, amorphous silica / boria, amorphous alumina / zirconia, amorphous alumina / magnesia, amorphous At least one selected from alumina / titania, amorphous alumina / boria, amorphous zirconia / magnesia, amorphous zirconia / titania, amorphous zirconia / boria, amorphous magnesia / titania, amorphous magnesia / boria and amorphous titania / boria It is preferable to contain two kinds of acid nature binary oxides. The acidic binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder. The binder is not particularly limited as long as it is generally used for catalyst preparation, but is preferably selected from silica, alumina, magnesia, titania, zirconia, clay, or a mixture thereof.

  In the production method A described above, the carrier is composed of at least one of group VIa metals (molybdenum, chromium, tungsten, etc.) of the periodic table and group VIII metal (nickel, cobalt, palladium, platinum, etc.). At least one of them is supported to form a hydrocracking catalyst. These metals are responsible for hydrogenation ability, terminate the reaction in which the paraffinic compound is decomposed or branched by the acidic carrier, and play an important role in producing isoparaffin having an appropriate molecular weight and branched structure.

  As the amount of metal supported in the hydrocracking catalyst, the supported amount of Group VIa metal is 5 to 30% by mass per one type of metal, and the supported amount of Group VIII metal is 0.2 to 10% by mass per one type of metal. % Is preferred.

  Further, in the hydrocracking catalyst used in the production method A, molybdenum is contained in the range of 5 to 30% by mass as one or more metals of the Group VIa metal, and one or more of the Group VIII metals is contained. More preferably, the metal contains nickel in the range of 0.2 to 10% by mass.

  The hydrocracking catalyst composed of the above support and one or more metals of Group VIa metal and one or more metals of Group VIII metal is preferably used for hydrocracking in a sulfurized state. The sulfurization treatment can be performed by a known method.

(Hydrolysis process)
In the production method A, a raw material oil containing 50% by volume or more of slack wax in the presence of the hydrocracking catalyst has a hydrogen partial pressure of 0.1 to 14 MPa, preferably 1 to 14 MPa, more preferably 2 to 2. 7 MPa; average reaction temperature of 230 to 430 ° C., preferably 330 to 400 ° C., more preferably 350 to 390 ° C .; LHSV of 0.3 to 3.0 hr ⁻¹ , preferably 0.5 to 2.0 hr ⁻¹ ; Hydrogenolysis is performed at a hydrogen oil ratio of 50 to 14,000 scf / b, preferably 100 to 5000 scf / b.

  In such a hydrocracking process, isomerization to isoparaffin progresses in the process of cracking n-paraffin derived from slack wax in the raw material oil, thereby producing an isoparaffin component having a low pour point and a high viscosity index. At the same time, it breaks down aromatic compounds, which are inhibitors of high viscosity index contained in the feedstock, into monocyclic aromatic compounds, naphthene compounds and paraffin compounds, and inhibits high viscosity index. The polycyclic naphthene compound as a factor can be decomposed into a monocyclic naphthene compound or a paraffin compound. From the viewpoint of increasing the viscosity index, it is preferable that the raw material oil contains fewer compounds having a high boiling point and a low viscosity index.

Further, the decomposition rate for evaluating the progress of the reaction is expressed by the following formula:
(Decomposition rate (volume%)) = 100− (ratio of the fraction having a boiling point of 360 ° C. or more in the product (volume%))
In this way, the decomposition rate is preferably 3 to 90% by volume. When the decomposition rate is less than 3% by volume, isoparaffins are generated by decomposition and isomerization of high-molecular-weight n-paraffins having a high pour point contained in the feedstock, and hydrocracking of aromatics and polycyclic naphthenes with poor viscosity index. When the decomposition rate exceeds 90% by volume, the yield of the lubricating oil fraction decreases, which is not preferable.

(Distillation separation process)
Next, the lubricating oil fraction is distilled and separated from the cracked product oil obtained by the hydrocracking step. At this time, a fuel oil fraction may be obtained as a light component.

  The fuel oil fraction is a fraction obtained as a result of sufficient desulfurization and denitrogenation, and sufficient aromatic hydrogenation. Among these, the naphtha fraction has a high isoparaffin content, the kerosene fraction has a high smoke point, and the light oil fraction has a high cetane number.

  On the other hand, when hydrocracking in the lubricating oil fraction is insufficient, a part of it may be subjected to the hydrocracking process again. Further, in order to obtain a lubricating oil fraction having a desired kinematic viscosity, the lubricating oil fraction may be further distilled under reduced pressure. This vacuum distillation separation may be performed after the dewaxing treatment described below.

  In the evaporative separation step, a lubricant base oil called 70 Pale, SAE10, or SAE20 can be suitably obtained by distilling the cracked product oil obtained in the hydrocracking step under reduced pressure.

  A system that uses slack wax with lower viscosity as the feedstock is suitable for producing a large amount of 70 Pale and 10 SAE fractions, and a system that uses slack wax with a high viscosity within the above range as feedstock produces a lot of SAE20. Suitable for doing. However, even if a high-viscosity slack wax is used, conditions for generating a considerable amount of 70 Pale and SAE 10 can be selected depending on the progress of the decomposition reaction.

(Dewaxing process)
In the above-described distillation separation step, since the lubricating oil fraction fractionated from the cracked product oil has a high pour point, it is dewaxed to obtain a lubricating base oil having a desired pour point. The dewaxing treatment can be performed by a usual method such as a solvent dewaxing method or a contact dewaxing method. Among these, the solvent dewaxing method generally uses a mixed solvent of MEK and toluene, but may use a solvent such as benzene, acetone, MIBK or the like. In order to make the pour point of the dewaxed oil not more than −10 ° C., the solvent / oil ratio is 1 to 6 times, and the filtration temperature is −5 to −45 ° C., preferably −10 to −40 ° C. The wax removed here can be used again as a slack wax in the hydrocracking step.

  In the said manufacturing method, you may add a solvent refinement | purification process and / or a hydrorefining process to a dewaxing process. These additional treatments are performed in order to improve the ultraviolet stability and oxidation stability of the lubricating base oil, and can be carried out by a method used in a normal lubricating oil refining process.

  In the solvent purification, furfural, phenol, N-methylpyrrolidone or the like is generally used as a solvent, and a small amount of aromatic compounds, particularly polycyclic aromatic compounds remaining in the lubricating oil fraction are removed.

In addition, hydrorefining is performed to hydrogenate olefin compounds and aromatic compounds, and the catalyst is not particularly limited. However, at least one of Group VIa metals such as molybdenum, cobalt, nickel, etc. Using an alumina catalyst supporting at least one of the Group VIII metals, the reaction pressure (hydrogen partial pressure) is 7 to 16 MPa, the average reaction temperature is 300 to 390 ° C., and the LHSV is 0.5 to 4.0 hr ⁻¹ . Can be done below.

  Moreover, as a preferable example of the manufacturing method of the lubricating base oil according to the present invention, the following manufacturing method B can be mentioned.

That is, the production method B according to the present invention is:
A fifth step of hydrocracking and / or hydroisomerizing a feedstock containing paraffinic hydrocarbons in the presence of a catalyst;
A sixth step of dewaxing the product obtained in the fifth step or the lubricating oil fraction recovered from the product by distillation or the like;
Is provided.

  Hereinafter, the production method B will be described in detail.

(Raw oil)
In the production method B, a raw material oil containing paraffinic hydrocarbon is used. The “paraffinic hydrocarbon” referred to in the present invention means a hydrocarbon having a paraffin molecule content of 70% by mass or more. The carbon number of the paraffinic hydrocarbon is not particularly limited, but usually about 10 to 100 is used. The paraffinic hydrocarbon production method is not particularly limited, and various paraffinic hydrocarbons such as petroleum and synthetic can be used. Particularly preferable paraffinic hydrocarbons include a gas-liquid (GTL) process and the like. Synthetic waxes obtained (Fischer-Tropsch wax (FT wax), GTL wax, etc.) can be mentioned, among which FT wax is preferred. The synthetic wax is preferably a wax containing, as a main component, a normal paraffin having 15 to 80 carbon atoms, more preferably 20 to 50 carbon atoms.

The kinematic viscosity of the paraffinic hydrocarbon used in the preparation of the raw material oil can be appropriately selected according to the kinematic viscosity of the target lubricating base oil, but the low viscosity base oil is used as the lubricating base oil according to the present invention. To produce a relatively low viscosity paraffin having a kinematic viscosity at 100 ° C. of about ² to 25 mm ² / s, preferably about 2.5 to ²⁰ mm ² / s, more preferably about 3 to 15 mm ² / s. Series hydrocarbons are desirable. In addition, other properties of the paraffinic hydrocarbon are optional, but when the paraffinic hydrocarbon is a synthetic wax such as FT wax, the melting point is preferably 35 to 80 ° C, more preferably 50 to 80 ° C, More preferably, it is 60-80 degreeC. The oil content of the synthetic wax is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less. Further, the sulfur content of the synthetic wax is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and further preferably 0.0001% by mass or less.

  When the raw material oil is a mixed oil of the above synthetic wax and another raw material oil, the other raw material oil is not particularly limited as long as the ratio of the synthetic wax to the total amount of the mixed oil is 50% by volume or more. A heavy atmospheric distillation oil and / or a mixed oil of reduced pressure distillation oil is preferably used.

  Further, when the raw material oil is a mixed oil of the above synthetic wax and other raw material oils, the proportion of the synthetic wax in the mixed oil is more than 70% by volume from the viewpoint of producing a base oil having a high viscosity index. Preferably, 75% by volume or more is even more preferable. If the ratio is less than 70% by volume, the lubricating base oil to be obtained tends to increase the oil content such as aromatics and naphthenes and decrease the viscosity index of the lubricating base oil.

  On the other hand, heavy crude pressure distillation distillate and / or vacuum distillation distillate of crude oil used in combination with synthetic wax is used at a distillation temperature of 300 to 570 ° C. in order to keep the viscosity index of the lubricating base oil to be produced high. A fraction having a distillate component of 60% by volume or more in the range is preferable.

(catalyst)
The catalyst used in production method B is not particularly limited, but a catalyst in which at least one selected from Group VI metal and Group VIII metal of the periodic table as an active metal component is supported on a support containing aluminosilicate. Preferably used.

  Aluminosilicate refers to a metal oxide composed of three elements of aluminum, silicon, and oxygen. Further, other metal elements can be allowed to coexist within a range that does not hinder the effects of the present invention. In this case, the amount of the other metal element is preferably 5% by mass or less, and more preferably 3% by mass or less of the total amount of alumina and silica as the oxide. Examples of metal elements that can coexist include titanium, lanthanum, manganese, and the like.

The crystallinity of aluminosilicate can be estimated by the proportion of tetracoordinate aluminum atoms in all aluminum atoms, and this proportion can be measured by ²⁷ Al solid state NMR. As the aluminosilicate used in the present invention, the ratio of tetracoordinated aluminum to the total amount of aluminum is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. Hereinafter, an aluminosilicate in which the ratio of tetracoordinated aluminum to the total amount of aluminum is 50% by mass or more is referred to as “crystalline aluminosilicate”.

  As the crystalline aluminosilicate, so-called zeolite can be used. Preferable examples include Y-type zeolite, ultra-stable Y-type zeolite (USY-type zeolite), β-type zeolite, mordenite, ZSM-5, etc. Among them, USY zeolite is particularly preferable. In the present invention, one type of crystalline aluminosilicate may be used alone, or two or more types may be used in combination.

  Examples of a method for preparing a carrier containing crystalline aluminosilicate include a method of molding a mixture of crystalline aluminosilicate and a binder and firing the molded body. The binder to be used is not particularly limited, but alumina, silica, silica alumina, titania and magnesia are preferable, and alumina is particularly preferable. The use ratio of the binder is not particularly limited, but is usually preferably 5 to 99% by mass and more preferably 20 to 99% by mass based on the total amount of the molded body. 430-470 degreeC is preferable, as for the baking temperature of the molded object containing a crystalline aluminosilicate and a binder, 440-460 degreeC is more preferable, and 445-455 degreeC is more preferable. The firing time is not particularly limited, but is usually 1 minute to 24 hours, preferably 10 minutes to 20 hours, more preferably 30 minutes to 10 hours. Firing may be performed in an air atmosphere, but is preferably performed in an oxygen-free atmosphere such as a nitrogen atmosphere.

  Examples of the Group VI b metal supported on the carrier include chromium, molybdenum, tungsten, and the like. Specific examples of the Group VIII metal include cobalt, nickel, rhodium, palladium, iridium, platinum, and the like. It is done. These metals may be used individually by 1 type, or may be used in combination of 2 or more types. When two or more kinds of metals are combined, noble metals such as platinum and palladium may be combined, base metals such as nickel, cobalt, tungsten and molybdenum may be combined, or a noble metal and a base metal may be combined.

  Further, the loading of the metal on the carrier can be performed by information such as impregnation of the carrier into a solution containing the metal, ion exchange, and the like. The amount of the metal supported can be appropriately selected, but is usually 0.05 to 2% by mass, preferably 0.1 to 1% by mass based on the total amount of the catalyst.

(Hydrolysis / Hydroisomerization process)
In the production method B, the feedstock oil containing paraffinic hydrocarbon is hydrocracked / hydroisomerized in the presence of the catalyst. Such hydrocracking / hydroisomerization step can be performed using a fixed bed reactor. As conditions for hydrocracking / hydroisomerization, for example, the temperature is preferably 250 to 400 ° C., the hydrogen pressure is preferably 0.5 to 10 MPa, and the liquid space velocity (LHSV) of the feedstock is preferably 0.5 to 10 h ^−1. .

(Distillation separation process)
Next, the lubricating oil fraction is distilled and separated from the cracked product oil obtained by the hydrocracking / hydroisomerization step. In addition, since the distillation separation process in the manufacturing method B is the same as the distillation separation process in the manufacturing method A, the overlapping description is abbreviate | omitted here.

(Dewaxing process)
Subsequently, the lubricating oil fraction fractionated from the cracked product oil in the distillation separation step is dewaxed. Such a dewaxing step can be performed using a conventionally known dewaxing process such as solvent dewaxing or catalytic dewaxing. Here, if the substance having a boiling point of 370 ° C. or less present in the cracked / isomerized product oil is not separated from the high boiling point substance prior to dewaxing, depending on the use of the cracked / isomerized product oil, The compound may be dewaxed or a fraction having a boiling point of 370 ° C. or higher may be dewaxed.

  In solvent dewaxing, the hydroisomerized product is contacted with chilled ketone and acetone, and other solvents such as MEK, MIBK, and further cooled to precipitate the high pour point material as a waxy solid, which is precipitated with raffinate. Separate from a solvent-containing lubricating oil fraction. Further, the raffinate can be cooled with a scraped surface chiller to remove wax solids. Low molecular weight hydrocarbons such as propane can also be used for dewaxing. In this case, the cracked / isomerized product oil and the low molecular weight hydrocarbon are mixed and at least a part thereof is vaporized to decompose / isomerize. The product oil is further cooled to precipitate the wax. The wax is separated from the raffinate by filtration, membrane or centrifugation. Thereafter, the solvent is removed from the raffinate, and the raffinate is fractionally distilled to obtain the target lubricating base oil.

  In the case of catalytic dewaxing (catalyst dewaxing), the cracked / isomerized product oil is reacted with hydrogen in the presence of a suitable dewaxing catalyst under conditions effective to lower the pour point. In catalytic dewaxing, some of the high-boiling substances in the cracking / isomerization product are converted to low-boiling substances, the low-boiling substances are separated from the heavier base oil fraction, and the base oil fraction is fractionated. Two or more kinds of lubricating base oils are obtained. The low-boiling substances can be separated before obtaining the target lubricating base oil or during fractional distillation.

  The dewaxing catalyst is not particularly limited as long as it can lower the pour point of the cracked / isomerized product oil, but the desired lubricating base oil is obtained from the cracked / isomerized product oil in a high yield. Those that can be used are preferred. As such a dewaxing catalyst, a shape selective molecular sieve (molecular sieve) is preferable, and specifically, ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 ( And theta aluminophosphates (SAPO) and the like. These molecular sieves are preferably used in combination with a catalytic metal component, and more preferably in combination with a noble metal. A preferable combination includes, for example, a composite of platinum and H-mordenite.

The dewaxing conditions are not particularly limited, but the temperature is preferably 200 to 500 ° C., and the hydrogen pressure is preferably 10 to 200 bar (1 MPa to 20 MPa). In the case of a flow-through reactor, the H ₂ treatment rate is preferably 0.1 to 10 kg / l / hr, and the LHSV is preferably 0.1 to 10 ^{−1 and} more preferably 0.2 to 2.0 h ^−1. . Dewaxing refers to a substance having an initial boiling point of 350 to 400 ° C., usually 40% by mass or less, preferably 30% by mass or less, contained in the cracked / isomerized product oil, having a boiling point lower than the initial boiling point. It is preferable to carry out the conversion to a substance having the same.

  As mentioned above, although the manufacturing method A and the manufacturing method B which are the preferable manufacturing methods of the lubricant base oil concerning this invention were demonstrated, the manufacturing method of the lubricant base oil concerning this invention is not limited to these. For example, in the above production method A, synthetic waxes such as FT wax and GTL wax may be used instead of slack wax. In the production method B, a raw material oil containing slack wax (preferably slack wax A, B) may be used. Furthermore, in each of the production methods A and B, slack wax (preferably slack wax A and B) and synthetic wax (preferably FT wax and GTL wax) may be used in combination.

  In addition, when the raw material oil used when manufacturing the lubricating base oil according to the present invention is a mixed oil of the above-described slack wax and / or synthetic wax and a raw material oil other than these waxes, slack wax The content of the synthetic wax is preferably 50% by mass or more based on the total amount of the raw material oil.

  The raw material oil for producing the lubricating base oil according to the present invention is a raw material oil containing slack wax and / or synthetic wax, and the oil content is preferably 60% by mass or less, more preferably 50% by mass. % Or less, more preferably 25% by mass or less.

  Further, the content of the saturated component in the lubricating base oil according to the present invention is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating base oil. In addition, the ratio of the cyclic saturated component in the saturated component is preferably 40% by mass or less, more preferably 0.1 to 40% by mass, still more preferably 2 to 30% by mass, and still more preferably 5 to 5% by mass. It is 25 mass%, Most preferably, it is 10-21 mass%. By satisfying the above conditions for the content of the saturated component and the ratio of the cyclic saturated component in the saturated component, the viscosity-temperature characteristics and thermal / oxidative stability can be achieved at a higher level, and the lubrication When an additive is blended in the oil base oil, the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricant base oil. Furthermore, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in friction reduction effect and an improvement in energy saving.

  In addition, when content of a saturated part is less than 90 mass%, it exists in the tendency for a viscosity-temperature characteristic, thermal / oxidation stability, and a friction characteristic to become inadequate. Moreover, when the ratio of the cyclic | annular saturated part to a saturated part exceeds 40 mass%, when an additive is mix | blended with lubricating base oil, it exists in the tendency for the effectiveness of the said additive to fall. Furthermore, when the ratio of the cyclic saturated component to the saturated component is less than 0.1% by mass, when the additive is blended with the lubricating base oil, the solubility of the additive is reduced and the lubricating base oil The effective amount of the additive dissolved and retained tends to decrease, and the function of the additive cannot be effectively obtained. Further, the content of the saturated component may be 100% by mass, but is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, from the viewpoint of reducing the production cost and improving the solubility of the additive. More preferably, it is 99 mass% or less, Most preferably, it is 98.5 mass% or less.

  In the lubricating base oil according to the present invention, the ratio of the cyclic saturated component in the saturated component is 40% by mass or less is equivalent to the non-cyclic saturated component in the saturated component being 60% by mass or more. . Here, the non-cyclic saturated component includes both a linear paraffin component and a branched paraffin component. The proportion of each paraffin component in the lubricating base oil according to the present invention is not particularly limited, but the proportion of the branched paraffin component is preferably 55 to 99 mass%, more preferably 57. It is 5-96 mass%, More preferably, it is 60-95 mass%, More preferably, it is 70-92 mass%, Most preferably, it is 80-90 mass%. When the ratio of the branched paraffin content in the lubricating base oil satisfies the above conditions, the viscosity-temperature characteristics and thermal / oxidative stability can be further improved, and an additive is added to the lubricating base oil. In this case, the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held. The proportion of linear paraffin in the lubricating base oil is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, based on the total amount of the lubricating oil base oil. It is. When the ratio of the straight-chain paraffin satisfies the above conditions, a lubricating base oil having more excellent low-temperature viscosity characteristics can be obtained.

  Further, in the lubricating base oil according to the present invention, the content of the saturated component of one ring and the saturated component of two or more rings in the saturated component is not particularly limited, but the ratio of the saturated component of two or more rings in the saturated component is It is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, particularly preferably 5% by mass or more, and 40% by mass. The content is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 11% by mass or less. Further, the percentage of saturated one ring in the saturated portion may be 0% by mass, preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4%. Further, it is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 11% by mass or less.

Further, in the lubricating base oil according to the present invention, the ratio of the monocyclic saturated component of the mass contained in the cyclic saturated components (M _A) and 2 rings or more saturated components mass _{(M B) (M A /} M B ) Is preferably 20 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less. _Although it may be a 0 M A / _{M B,} preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.5 or more. By the above condition is satisfied M A _/ M _B, the viscosity - a temperature characteristic and heat and oxidation stability can be further compatible at a high level.

Moreover, in the lubricating base oil according to the present invention, the ratio (M _A / M _c ) between the mass of the monocyclic saturated component (M _A ) and the mass of the bicyclic saturated component (M _c ) contained in the cyclic saturated component is , Preferably 3 or less, more preferably 1.5 or less, still more preferably 1.3 or less, particularly preferably 1.2 or less. _Although it may be a the _M A / M _c 0, preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.5 or more. By satisfying the above conditions for M _A / M _c , the viscosity-temperature characteristics and the heat / oxidation stability can be achieved at a higher level.

  In addition, content of the saturated part said by this invention means the value (unit: mass%) measured based on ASTM D 2007-93.

  Further, the ratios of the cyclic saturated component, the single ring saturated component, the two or more saturated components and the non-cyclic saturated component in the saturated component as used in the present invention are naphthenic components measured in accordance with ASTM D 2786-91, respectively. (Measuring target: 1-ring to 6-ring naphthene, unit: mass%) and alkane content (unit: mass%).

In addition, the linear paraffin content in the lubricating base oil referred to in the present invention is the gas chromatographic analysis of the saturated content separated and separated by the method described in ASTM D 2007-93 under the following conditions. The value obtained by converting the measured value when the linear paraffin content in the saturated content is identified and quantified based on the total amount of the lubricating base oil is meant. In the identification and quantification, a mixed sample of straight-chain paraffin having 5 to 50 carbon atoms is used as a standard sample, and the straight-chain paraffin content in the saturated portion is the total peak area value of the chromatogram (in the diluent). It is determined as the ratio of the sum of peak area values corresponding to each linear paraffin to (excluding the peak area value derived from).
(Gas chromatography conditions)
Column: non-polar liquid phase column (length 25 mm, inner diameter 0.3 mmφ, liquid phase film thickness 0.1 μm)
Temperature rising condition: 50 ° C. to 400 ° C. (temperature rising rate: 10 ° C./min)
Carrier gas: helium (linear velocity: 40 cm / min)
Split ratio: 90/1
Sample injection amount: 0.5 μL (injection amount of sample diluted 20 times with carbon disulfide)

  The ratio of branched paraffin in the lubricating base oil is the difference between the non-cyclic saturated content in the saturated content and the linear paraffin content in the saturated content, converted based on the total amount of the lubricating base oil. Means the value.

  In the case of a method for separating saturated components, or a compositional analysis of cyclic saturated components, non-cyclic saturated components, etc., a similar method can be used in which similar results can be obtained. For example, in addition to the above, a method described in ASTM D 2425-93, a method described in ASTM D 2549-91, a method using high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like can be given.

Also, the aromatic content in the lubricating base oil according to the present _{invention,% C A,% C P} /% C N, and although the iodine value is not particularly limited as long as the above conditions are satisfied, lubricating base oils the total amount Is preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, particularly preferably 3% by mass or less, and preferably 0.1% by mass or more, more preferably Is 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more. If the aromatic content exceeds the above upper limit, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to decrease. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Moreover, the lubricating base oil according to the present invention may not contain an aromatic component, but by further increasing the solubility of the additive by setting the aromatic content to the above lower limit or more. Can do.

  In addition, the aromatic component as used in the field of this invention means the value measured based on ASTM D 2007-93. In general, the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols and naphthols. Aromatic compounds having atoms are included.

  The viscosity index of the lubricating base oil according to the present invention is preferably 110 or more. When the viscosity index is less than the lower limit, viscosity-temperature characteristics, thermal / oxidation stability, and further volatilization prevention properties tend to decrease. The preferred range of the viscosity index of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, and will be described in detail later.

Other properties of the lubricating base oil according to the present _{invention,% C A,% C P} /% C N, and although the iodine value is not particularly limited as long as each of the above conditions are satisfied, the lubricating oil according to the present invention The base oil preferably has various properties shown below.

  The sulfur content in the lubricating base oil according to the present invention depends on the sulfur content of the raw material. For example, when a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like is used, a lubricating base oil that does not substantially contain sulfur can be obtained. In addition, when using raw materials containing sulfur such as slack wax obtained in the refining process of the lubricating base oil and microwax obtained in the refining process, the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it. In the lubricating base oil according to the present invention, the content of sulfur is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, from the viewpoint of further improvement in thermal and oxidation stability and low sulfur content. More preferably, it is more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.

  Further, from the viewpoint of cost reduction, it is preferable to use slack wax or the like as a raw material. In that case, the sulfur content in the obtained lubricating base oil is preferably 50 ppm by mass or less, and preferably 10 ppm by mass or less. More preferred. In addition, the sulfur content as used in the field of this invention means the sulfur content measured based on JISK2541-1996.

  The nitrogen content in the lubricating base oil according to the present invention is not particularly limited, but is preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, and further preferably 1 ppm by mass or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease. In addition, the nitrogen content as used in the field of this invention means the nitrogen content measured based on JISK2609-1990.

In addition, the kinematic viscosity of the lubricating base oil according to the present invention is not particularly limited as long as the% C _A ,% C _P /% C _N , and iodine value satisfy the above-mentioned conditions, but the kinematic viscosity at 100 ° C. is , Preferably 1.5 to ²⁰ mm ² / s, more preferably 2.0 to 11 mm ² / s. When the kinematic viscosity at 100 ° C. of the lubricating base oil is less than 1.5 mm ² / s, it is not preferable in terms of evaporation loss. In addition, when trying to obtain a lubricating base oil having a kinematic viscosity at 100 ° C. exceeding 20 mm ² / s, the yield decreases, and the decomposition rate can be increased even when heavy wax is used as a raw material. Since it becomes difficult, it is not preferable.

In the present invention, it is preferable to use a lubricating base oil having a kinematic viscosity at 100 ° C. in the following range by distillation or the like.
(I) less than the kinematic viscosity at 100 ° C. is 1.5 mm ² / s or more 3.5 mm ² / s, more preferably kinematic viscosity at 2.0 to 3.0 mm ² / s lubricating base oils (II) 100 ° C. There 3.0 mm ² / s or more 4.5mm less than ² / s, more preferably a kinematic viscosity at 3.5~4.1mm ² / s lubricating base oil (III) 100 ℃ 4.5~20mm ² / s, more preferably 4.8 to 11 mm ² / s, particularly preferably 5.5 to 8.0 mm ² / s.

Moreover, the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is preferably 6.0 to 80 mm ² / s, more preferably 8.0 to 50 mm ² / s. In the present invention, it is preferred that a lubricating oil fraction having a kinematic viscosity at 40 ° C. in the following range is fractionated by distillation or the like and used.
(IV) less than the kinematic viscosity at 40 ° C. is 6.0 mm ² / s or more 12 mm ² / s, more preferably 8.0~12mm ² / s lubricating base oil (V) kinematic viscosity at 40 ° C. is 12 mm ² / More than s and less than 28 mm < ² > / s, more preferably 13-19 mm < ² > / s lubricating base oil (VI) The kinematic viscosity at 40 [deg.] C. is 28-50 mm < ² > / s, more preferably 29-45 mm < ² > / s, particularly preferred. Is a lubricating base oil of 30 to 40 mm ² / s.

The above lubricating base oils (I) and (IV) are compared with conventional lubricating base oils with the same viscosity grade by satisfying the above conditions for% C _A ,% C _P /% C _N and iodine value, respectively. In particular, the low-temperature viscosity characteristics are excellent, and the viscosity resistance and stirring resistance can be remarkably reduced. Moreover, the BF viscosity in -40 degreeC can be 2000 mPa * s or less by mix | blending a pour point depressant. The BF viscosity at −40 ° C. means the viscosity measured according to JPI-5S-26-99.

In addition, the lubricating base oils (II) and (V) described above are conventional lubricating base oils having the same viscosity grade because% C _A ,% C _P /% C _N , and iodine value satisfy the above-mentioned conditions. In particular, it is excellent in low-temperature viscosity characteristics, volatilization prevention properties and lubricity. For example, in the lubricating base oils (II) and (V), the CCS viscosity at −35 ° C. can be set to 3000 mPa · s or less.

In addition, the lubricating base oils (III) and (VI) described above are conventional lubricating base oils having the same viscosity grade because% C _A ,% C _P /% C _N , and iodine value satisfy the above conditions, respectively. Compared with, it is excellent in low temperature viscosity characteristics, volatilization prevention, thermal / oxidation stability and lubricity.

  The viscosity index of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but the viscosity index is 110 or more in any of the lubricating base oils (I) to (VI). be able to. The viscosity index of the lubricating oils (I) and (IV) is preferably 110 to 135, more preferably 115 to 130, and still more preferably 120 to 130. The viscosity index of the lubricating base oils (II) and (V) is preferably 125 to 160, more preferably 130 to 150, and still more preferably 135 to 150. Further, the viscosity index of the lubricating base oils (III) and (VI) is preferably 135 to 180, more preferably 140 to 160. When the viscosity index is less than the lower limit, viscosity-temperature characteristics, thermal / oxidation stability, and further volatilization prevention properties tend to decrease. On the other hand, when the viscosity index exceeds the upper limit, the low-temperature viscosity characteristics tend to decrease.

  In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283-1993.

  Further, the refractive index at 20 ° C. of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, and for example, the refractive index at 20 ° C. of the lubricating base oils (I) and (IV). Is preferably 1.440 to 1.461, more preferably 1.442 to 1.460, and still more preferably 1.445 to 1.459. The refractive index of the lubricating base oils (II) and (V) at 20 ° C. is preferably 1.450 to 1.465, more preferably 1.452 to 1.463, and still more preferably 1.453 to 1.462. The refractive index of the lubricating base oils (III) and (VI) at 20 ° C. is preferably 1.455 to 1.469, more preferably 1.456 to 1.468, and still more preferably 1.457 to 1.467. If the refractive index exceeds the above upper limit, the viscosity-temperature characteristics and thermal / oxidative stability of the lubricating base oil tend to be reduced, and further, the volatilization preventing properties and low-temperature viscosity characteristics tend to deteriorate. When an additive is blended with the additive, the effectiveness of the additive tends to decrease.

  Further, the pour point of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil. For example, the pour point of the lubricating base oils (I) and (IV) is preferably −10. ° C or lower, more preferably -12.5 ° C or lower, still more preferably -15 ° C or lower. The pour points of the lubricating base oils (II) and (V) are preferably −10 ° C. or lower, more preferably −15 ° C. or lower, and still more preferably −17.5 ° C. or lower. The pour point of the lubricating base oils (III) and (VI) is preferably −10 ° C. or lower, more preferably −12.5 ° C. or lower, and still more preferably −15 ° C. or lower. When the pour point exceeds the upper limit, the low temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease. In addition, the pour point as used in the field of this invention means the pour point measured based on JISK2269-1987.

  Further, the CCS viscosity of the lubricating base oil according to the present invention at −35 ° C. depends on the viscosity grade of the lubricating base oil, but for example, the lubricating base oils (I) and (IV) at −35 ° C. The CCS viscosity is preferably 1000 mPa · s or less. The CCS viscosity at −35 ° C. of the lubricating base oils (II) and (V) is preferably 3000 mPa · s or less, more preferably 2400 mPa · s or less, still more preferably 2200 mPa · s or less, and particularly preferably 2000 mPa · s. -S or less. Further, the CCS viscosity of the lubricating base oils (III) and (VI) at −35 ° C. is preferably 15000 mPa · s or less, more preferably 10000 mPa · s or less, and further preferably 8000 mPa · s or less. When the CCS viscosity at −35 ° C. exceeds the upper limit, the low-temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease. In addition, the CCS viscosity at −35 ° C. in the present invention means a viscosity measured according to JIS K 2010-1993.

Further, the density (ρ ₁₅ , unit: g / cm ³ ) of the lubricating base oil according to the present invention at 15 ° C. depends on the viscosity grade of the lubricating base oil, but the value of ρ represented by the following formula (1) It is preferable that ρ ₁₅ ≦ ρ.
ρ = 0.0025 × kv100 + 0.820 (1)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil at 100 ° C. ]

When ρ ₁₅ > ρ, the viscosity-temperature characteristics and thermal / oxidation stability, volatilization prevention properties and low-temperature viscosity characteristics tend to decrease, and additives are added to the lubricating base oil. In some cases, the effectiveness of the additive tends to decrease.

For example, ρ ₁₅ of the lubricating base oils (I) and (IV) is preferably 0.825 g / cm ³ or less, more preferably 0.820 g / cm ³ or less. The ρ ₁₅ of the lubricating base oils (II) and (V) is preferably 0.835 g / cm ³ or less, more preferably 0.830 g / cm ³ or less. The ρ ₁₅ of the lubricating base oils (III) and (VI) is preferably 0.840 g / cm ³ or less, more preferably 0.835 g / cm ³ or less.

  In addition, the density in 15 degreeC said by this invention means the density measured in 15 degreeC based on JISK2249-1995.

Further, the aniline point (AP (° C.)) of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but is not less than the value of A represented by the following formula (2). It is preferable that ≧ A.
A = 4.1 × kv100 + 97 (2)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil at 100 ° C. ]

  When AP <A, viscosity-temperature characteristics and thermal / oxidative stability, volatilization prevention properties and low-temperature viscosity characteristics tend to decrease, and when additives are added to the lubricating base oil In addition, the effectiveness of the additive tends to decrease.

  For example, the AP of the lubricating base oils (I) and (IV) is preferably 108 ° C. or higher, more preferably 110 ° C. or higher, and still more preferably 112 ° C. or higher. The AP of the lubricating base oils (II) and (V) is preferably 113 ° C. or higher, more preferably 116 ° C. or higher, still more preferably 118 ° C. or higher, and particularly preferably 120 ° C. or higher. The AP of the lubricating base oils (III) and (VI) is preferably 125 ° C. or higher, more preferably 127 ° C. or higher, and still more preferably 128 ° C. or higher. In addition, the aniline point as used in the field of this invention means the aniline point measured based on JISK2256-1985.

  Further, the NOACK evaporation amount of the lubricating base oil according to the present invention is not particularly limited. For example, the NOACK evaporation amount of the lubricating base oils (I) and (IV) is preferably 20% by mass or more, more preferably. Is 25 mass% or more, more preferably 30 or more, preferably 50 mass% or less, more preferably 45 mass% or less, and still more preferably 42 mass% or less. The NOACK evaporation amount of the lubricating base oils (II) and (V) is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 20%. It is not more than mass%, more preferably not more than 16 mass%, still more preferably not more than 15 mass%, particularly preferably not more than 14 mass%. Further, the NOACK evaporation amount of the lubricating base oils (III) and (VI) is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 6%. It is at most 4% by mass, more preferably at most 4% by mass. When the NOACK evaporation amount is the lower limit value, it tends to be difficult to improve the low temperature viscosity characteristics. Further, when the NOACK evaporation amount exceeds the upper limit value, when the lubricating base oil is used as the lubricating oil for an internal combustion engine, the evaporation loss amount of the lubricating oil increases, and accordingly, catalyst poisoning is promoted. Therefore, it is not preferable. In addition, the NOACK evaporation amount as used in the field of this invention means the evaporation loss amount measured based on ASTM D 5800-95.

  Further, the distillation properties of the lubricating base oil according to the present invention are preferably gas chromatography distillation, wherein the initial boiling point (IBP) is 290 to 440 ° C. and the end point (FBP) is 430 to 580 ° C., and such a distillation range. The base oils (I) to (III) and (IV) to (VI) having the preferred viscosity ranges described above are obtained by rectifying one or more fractions selected from the fractions in be able to.

  For example, regarding the distillation properties of the lubricating base oils (I) and (IV), the initial boiling point (IBP) is preferably 260 to 360 ° C, more preferably 300 to 350 ° C, and still more preferably 310 to 350 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 320-400 degreeC, More preferably, it is 340-390 degreeC, More preferably, it is 350-380 degreeC. The 50% distillation point (T50) is preferably 350 to 430 ° C, more preferably 360 to 410 ° C, and still more preferably 370 to 400 ° C. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 380-460 degreeC, More preferably, it is 390-450 degreeC, More preferably, it is 400-440 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 420-520 degreeC, More preferably, it is 430-500 degreeC, More preferably, it is 440-480 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 50-100 degreeC, More preferably, it is 55-85 degreeC, More preferably, it is 60-70 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 100-250 degreeC, More preferably, it is 110-220 degreeC, More preferably, it is 120-200 degreeC. Moreover, T10-IBP becomes like this. Preferably it is 10-80 degreeC, More preferably, it is 15-60 degreeC, More preferably, it is 20-50 degreeC. Moreover, FBP-T90 becomes like this. Preferably it is 10-80 degreeC, More preferably, it is 15-70 degreeC, More preferably, it is 20-60 degreeC.

  Moreover, regarding the distillation properties of the lubricating base oils (II) and (V), the initial boiling point (IBP) is preferably 300 to 380 ° C, more preferably 320 to 370 ° C, still more preferably 330 to 360 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 340-420 degreeC, More preferably, it is 350-410 degreeC, More preferably, it is 360-400 degreeC. The 50% distillation point (T50) is preferably 380 to 460 ° C, more preferably 390 to 450 ° C, and still more preferably 400 to 460 ° C. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 440-500 degreeC, More preferably, it is 450-490 degreeC, More preferably, it is 460-480 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 460-540 degreeC, More preferably, it is 470-530 degreeC, More preferably, it is 480-520 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 50-100 degreeC, More preferably, it is 60-95 degreeC, More preferably, it is 80-90 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 100-250 degreeC, More preferably, it is 120-180 degreeC, More preferably, it is 130-160 degreeC. Moreover, T10-IBP becomes like this. Preferably it is 10-70 degreeC, More preferably, it is 15-60 degreeC, More preferably, it is 20-50 degreeC. Moreover, FBP-T90 becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-40 degreeC, More preferably, it is 25-35 degreeC.

  Further, regarding the distillation properties of the lubricating base oils (III) and (VI), the initial boiling point (IBP) is preferably 320 to 480 ° C, more preferably 350 to 460 ° C, still more preferably 380 to 440 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 420-500 degreeC, More preferably, it is 430-480 degreeC, More preferably, it is 440-460 degreeC. The 50% distillation point (T50) is preferably 440 to 520 ° C, more preferably 450 to 510 ° C, and still more preferably 460 to 490 ° C. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 470-550 degreeC, More preferably, it is 480-540 degreeC, More preferably, it is 490-520 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 500-580 degreeC, More preferably, it is 510-570 degreeC, More preferably, it is 520-560 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 50-120 degreeC, More preferably, it is 55-100 degreeC, More preferably, it is 55-90 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 100-250 degreeC, More preferably, it is 110-220 degreeC, More preferably, it is 115-200 degreeC. Moreover, T10-IBP becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 15-90 degreeC, More preferably, it is 20-50 degreeC. Moreover, FBP-T90 becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-40 degreeC, More preferably, it is 25-35 degreeC.

  In each of the lubricating base oils (I) to (VI), IBP, T10, T50, T90, FBP, T90-T10, FBP-IBP, T10-IBP, and FBP-T90 are set to the above preferable ranges. Further, it is possible to further improve the low temperature viscosity and further reduce the evaporation loss. In addition, about each of T90-T10, FBP-IBP, T10-IBP, and FBP-T90, when the distillation range is made too narrow, the yield of lubricating base oil is deteriorated, which is not preferable in terms of economy. .

  In the present invention, IBP, T10, T50, T90 and FBP mean distillate points measured in accordance with ASTM D 2887-97, respectively.

  Further, the residual metal content in the lubricating base oil according to the present invention is derived from the metal content contained in the catalyst and raw materials that are inevitably mixed in the manufacturing process, but it is preferable that the residual metal content be sufficiently removed. . For example, the contents of Al, Mo, and Ni are each preferably 1 mass ppm or less. If the content of these metals exceeds the above upper limit, the function of the additive blended with the lubricating base oil tends to be inhibited.

  In addition, the residual metal content as used in the field of this invention means the metal content measured based on JPI-5S-38-2003.

In addition, according to the lubricating base oil of the present invention, excellent thermal / oxidative stability can be achieved by satisfying the above conditions for% C _A ,% C _P /% C _N , and iodine value, respectively. However, it is preferable to show the RBOT life shown below according to the kinematic viscosity. For example, the RBOT life of the lubricating base oils (I) and (IV) is preferably 300 min or more, more preferably 320 min or more, and further preferably 330 min or more. The RBOT life of the lubricating base oils (II) and (V) is preferably 350 min or more, more preferably 370 min or more, and further preferably 380 min or more. The RBOT life of the lubricating base oils (III) and (VI) is preferably 400 min or more, more preferably 410 min or more, and further preferably 420 min or more. When the RBOT life is less than the lower limit, the viscosity-temperature characteristics and thermal / oxidative stability of the lubricating base oil tend to decrease. Further, when an additive is blended in the lubricating base oil, The effectiveness of the additive tends to decrease.

  The RBOT life as used herein refers to a composition in which 0.2% by mass of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) is added to a lubricating base oil. It means the RBOT value measured according to JIS K 2514-1996.

  In the metalworking oil composition of the present invention, the lubricating base oil according to the present invention may be used alone, and the lubricating base oil according to the present invention may be one or more of other base oils. You may use together. When the lubricating base oil according to the present invention is used in combination with another base oil, the ratio of the lubricating base oil according to the present invention in the mixed base oil is preferably 30% by mass or more. More preferably, the content is 50% by mass or more, and further preferably 70% by mass or more.

Although it does not restrict | limit especially as another base oil used together with the lubricating base oil concerning this invention, As a mineral oil type | system | group base oil, solvent refined mineral oil whose kinematic viscosity in 100 degreeC is 1-100 mm < ² > / s, for example, hydrogen Examples include hydrocracked mineral oil, hydrorefined mineral oil, and solvent dewaxing base oil.

  Synthetic base oils include poly α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridec Decyl adipate, di-2-ethylhexyl sebacate, etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl Examples thereof include diphenyl ether and polyphenyl ether, and among them, poly α-olefin is preferable. As the poly α-olefin, typically, an oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those. Of the hydrides.

  The production method of poly α-olefin is not particularly limited. For example, Friedel-Crafts catalyst containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester. And a method of polymerizing α-olefin in the presence of a polymerization catalyst such as

  In addition, the metalworking oil composition of the present invention contains at least one lubricity improver selected from esters, alcohols, carboxylic acids, and compounds containing phosphorus and / or sulfur as constituent elements.

  The alcohol constituting the ester as the lubricity improver may be a monohydric alcohol or a polyhydric alcohol. The carboxylic acid constituting the ester may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol, one having 1 to 24 carbon atoms is usually used, and such an alcohol may be linear or branched. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched octanol, and linear Or branched nonanol, linear or branched decanol, linear or branched undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetra Decanol, 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 or branched tricosanol, linear or branched Tetracosanol, and mixtures thereof of.

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

  Among these, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc. ) And dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2 3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols, and mixtures thereof such as mannitol and the like are more preferable. More preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof.

  The monobasic acid constituting the ester is usually a fatty acid having 6 to 24 carbon atoms, which may be linear or branched, and may be saturated or unsaturated. Specifically, for example, 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 a saturated fatty acid such as branched heneicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid; 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 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 heneicosenoic acid, linear or branched Docosenoic acid, linear or branched tricosenoic acid, unsaturated fatty acids such as linear or branched tetracosenoic acid, and mixtures thereof. 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 saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid Acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid; linear or Branched hexenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid, linear or branched decenedioic acid, linear or branched undecenedioic acid , Linear or branched dodecenedioic acid, linear or branched tridecenedioic acid, linear Or branched tetradecene diacid, linear or branched heptadecenoic acid, straight-chain or branched hexadecene diacid; include and mixtures thereof.

In this invention, ester by the combination of arbitrary alcohol and carboxylic acid can be used, and it does not specifically limit. Specifically, esters shown in the following (i) to (vii) can be preferably used.
(I) ester of monohydric alcohol and monobasic acid (ii) ester of polyhydric alcohol and monobasic acid (iii) ester of monohydric alcohol and polybasic acid (iv) polyhydric alcohol and polybasic acid (V) Esters of monohydric alcohols and mixed alcohols of polyhydric alcohols with polybasic acids (vi) Esters of polyhydric alcohols with monobasic acids and mixed carboxylic acids of polybasic acids (vii) Monohydric alcohols and Ester of mixed alcohol of polyhydric alcohol and mixed carboxylic acid of monobasic acid and polybasic acid.

  When a polyhydric alcohol is used as the alcohol component, the ester may be a complete ester in which all of the hydroxyl groups in the polyhydric alcohol are esterified. It may be a partial ester remaining as it is. In addition, 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. May be a partial ester remaining.

  As the ester used in the present invention, any of the above-mentioned esters can be used. Among them, (i) an ester of a monohydric alcohol and a monobasic acid, and (iii) An ester of a monohydric alcohol and a polybasic acid is preferred, (i) an ester of a monohydric alcohol and a monobasic acid is more preferred, (i) an ester of a monohydric alcohol and a monobasic acid, and (iii) a monohydric alcohol Most preferably, an ester with a polybasic acid is used in combination.

  (I) The total carbon number of the ester of monohydric alcohol and monobasic acid preferably used in the present invention is not particularly limited, but an ester having a lower limit of the total carbon number of 7 or more is preferred, and an ester of 9 or more is preferred. More preferred is an ester of 11 or more. Further, an ester having an upper limit of the total carbon number of 26 or less is preferred, an ester of 24 or less is more preferred, and an ester of 22 or less is most preferred. 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. If the total carbon number, the carbon number of the alcohol and the carbon number of the monobasic acid each exceed the upper limit, the possibility of increasing the occurrence of stain and corrosion increases, and the fluidity is lost in winter. There is a tendency that the risk of becoming difficult becomes greater, or that the solubility in the lubricating base oil decreases and the risk of precipitation increases. Further, when the total carbon number, the carbon number of the alcohol, and the carbon number of the monobasic acid are each lower than the lower limit value, the lubricity tends to be insufficient, and the working environment is deteriorated by odor. There is a fear.

The form of the ester of (iii) monohydric alcohol and polybasic acid preferably used in the present invention is not particularly limited, but is preferably a diester represented by the following general formula (1) or an ester of trimellitic acid. .
R ¹ —O—CO— (CH ₂ ) _n —CO—O—R ² (1)
[Wherein, R ¹ and R ² may be the same or different and each represents a hydrocarbon group, and n represents an integer of 4 to 8. ]

R ¹ and R ² in the general formula (1) each represent a hydrocarbon group, and the hydrocarbon group preferably has 3 to 10 carbon atoms. If the hydrocarbon group has less than 3 carbon atoms, the lubricity improvement effect may not be expected, and the working environment may deteriorate due to odor. In addition, if the hydrocarbon group has more than 10 carbon atoms, there is a greater risk of increasing the occurrence of stains and corrosion, and there is a greater risk of losing fluidity and difficulty in handling in winter. There is a tendency that the risk of precipitation decreases and the possibility of precipitation increases.

Examples of the hydrocarbon group represented by R ¹ and R ² in the general formula (1) include an alkyl group, an alkenyl group, an alkylcycloalkyl group, an alkylphenyl group, and a phenylalkyl group, and an alkyl group is particularly preferable.

When R ¹ and R ² are alkyl groups, the alkyl group may be either a linear alkyl group or a branched alkyl group, and a linear alkyl group and a branched alkyl group are mixed in the same molecule. A branched alkyl group is preferred.

Specific examples of the alkyl group represented by R ¹ and R ² include a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, and a linear or branched hexyl group. 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.

  Moreover, n in General formula (1) shows the integer of 4-8. In addition, when n exceeds 8, the possibility of increasing the occurrence of stains and corrosion increases, the possibility of losing fluidity and difficulty in handling in winter increases, and the solubility in lubricating base oil decreases. There is a tendency that the risk of precipitation increases. Moreover, when n is less than 4, there is a possibility that the improvement effect of lubricity may not be expected, and the working environment tends to deteriorate due to odor. Furthermore, a diester in which n is 4 or 6 is particularly preferable from the viewpoint of availability of raw materials and price.

  The diester represented by the general formula (1) can be obtained by an arbitrary method. For example, the diester represented directly by a carbonic acid number of 6 to 10 (adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid in order from the carbon number of 6). Examples thereof include a method of esterifying a chain saturated dicarboxylic acid or a derivative thereof and an alcohol having 3 to 10 carbon atoms.

  Moreover, when ester is ester of trimellitic acid and monohydric alcohol, although carbon number of the said monohydric alcohol does not have a restriction | limiting in particular, C1-C10 is preferable, C1-C8 is more preferable, Carbon Numbers 1 to 6 are more preferable, and carbon numbers 1 to 4 are most preferable. When the number of carbon atoms of the monohydric alcohol exceeds 10, the possibility of increasing the occurrence of stains and corrosion increases, and the possibility of losing fluidity and difficulty in handling in winter increases. There is a tendency that the risk of precipitation decreases and the possibility of precipitation increases. The ester of trimellitic acid may be a partial ester (monoester or diester) or a complete ester (triester).

  Particularly preferred examples of esters used as lubricity improvers include, specifically, methyl laurate, butyl laurate, methyl stearate, butyl stearate, methyl oleate, butyl oleate, and adipic acid and carbon number. Examples include diesters with 4 to 10 alcohols.

  Examples of the alcohol used as the lubricity improver include monohydric alcohols and polyhydric alcohols exemplified in the description of the ester. Among them, monohydric alcohols and dihydric alcohols are preferable, and monohydric alcohols are used alone. It is more preferable to use a monohydric alcohol and a dihydric alcohol in combination. Moreover, as a bihydric alcohol, what has an ether bond in a molecule | numerator is preferable.

  The number of carbon atoms of the monohydric alcohol and dihydric alcohol is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, and particularly preferably 9 or more. In addition, when carbon number of monohydric alcohol and dihydric alcohol is less than 6, there exists a tendency for lubricity to become inadequate and there exists a possibility that a working environment may deteriorate with an odor. Moreover, carbon number of monohydric alcohol and dihydric alcohol becomes like this. Preferably it is 20 or less, More preferably, it is 18 or less. When the number of carbons of monohydric alcohol and dihydric alcohol exceeds 20, the possibility of increasing the occurrence of stains and corrosion increases, and the possibility of losing fluidity and difficulty in handling in winter increases. There is a tendency that the solubility in oil decreases and the risk of precipitation increases.

  As a particularly preferable example of alcohol used as a lubricity improver, specifically, lauryl alcohol, myristyl alcohol, palmityl alcohol, oleyl alcohol, ethylene glycol 5-9 mer, propylene glycol 2-6 mer As well as mixtures of two or more of these.

  The carboxylic acid used as the lubricity improver may be a monobasic acid or a polybasic acid. Specific examples include monobasic acids and polybasic acids exemplified in the description of the ester. Among these, a monobasic acid is preferable from the viewpoint of excellent processability.

  The number of carbon atoms of the carboxylic acid used as the lubricity improver is preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more, from the viewpoint of more excellent lubricity improvement effect. Moreover, from the point which suppresses generation | occurrence | production of a stain or corrosion, carbon number of carboxylic acid becomes like this. Preferably it is 20 or less, More preferably, it is 18 or less, More preferably, it is 16 or less.

  Specific preferred examples of the carboxylic acid used as the lubricity improver include lauric acid, myristic acid, palmitic acid and oleic acid.

  The above ester, alcohol and carboxylic acid used as a lubricity improver are particularly excellent in oily effect. In the present invention, one of ester, alcohol, and carboxylic acid may be used alone as a lubricity improver, or a mixture of two or more kinds may be used. And monohydric alcohols are preferred, and esters are more preferred.

  The content of the ester, alcohol and carboxylic acid as the lubricity improver is preferably 0.1 to 70% by mass based on the total amount of the composition. That is, the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more from the viewpoint of the effect of improving lubricity. In addition, the content is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably from the viewpoint that if the content is too much, there is a possibility of increasing the occurrence of stain and corrosion. It is 50% by mass or less, more preferably 15% by mass or less, particularly preferably 12% by mass or less, and most preferably 10% by mass or less.

  Examples of the compound containing phosphorus and / or sulfur as constituent elements include a sulfur compound and a phosphorus compound described later. In addition, content here means the content, when using individually 1 type of ester, alcohol, or carboxylic acid, and when using it in combination of 2 or more types, total content is set. means.

  Moreover, as a sulfur compound used as a lubricity improver, dihydrocarbyl polysulfide, sulfide ester, sulfide mineral oil, zinc dithiophosphate compound, zinc dithiocarbamate compound, molybdenum dithiophosphate and molybdenum dithiocarbamate are preferably used.

Dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin, and a preferred example includes a compound represented by the following general formula (2).
R ³ —S _h —R ⁴ (2)
[In Formula (2), R ³ and R ⁴ may be the same or different, and each has a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. Represents an alkylaryl group having 6 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms, and h represents an integer of 2 to 6, preferably 2 to 5.]

Specific examples of R ³ and R ⁴ in the general formula (2) include n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched Undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group Linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched alkyl group such as linear or branched icosyl group; aryl group such as phenyl group or naphthyl group; tolyl group ( Includes all structural isomers , 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 group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (all structural isomers) Straight chain or branched octylphenyl group (including all structural isomers), straight chain or branched nonylphenyl group (including all structural isomers), straight chain or branched decylphenyl group (all ), Linear or branched undecylphenyl group (including all structural isomers), linear or branched dodecylphenyl group (including all structural isomers), xylyl group (all Including structural isomers), ethyl Methylphenyl group (including all structural isomers), diethylphenyl group (including all structural isomers), di (straight or branched) propylphenyl group (including all structural isomers), di (direct Chain or branched) butylphenyl group (including all structural isomers), methylnaphthyl group (including all structural isomers), ethylnaphthyl group (including all structural isomers), linear or branched propyl Naphthyl group (including all structural isomers), linear or branched butyl naphthyl group (including all structural isomers), dimethylnaphthyl group (including all structural isomers), ethylmethylnaphthyl group (all Including structural isomers), diethyl naphthyl group (including all structural isomers), di (linear or branched) propyl naphthyl group (including all structural isomers), di (straight or branched) butyl Naphthyl group (all Alkylaryl groups such as isomers); arylalkyl groups such as benzyl, phenylethyl groups (including all isomers), and phenylpropyl groups (including all isomers); . Among these, R ³ and R ⁴ in the general formula (2), propylene, 1-butene or an alkyl group has been 3 to 18 carbon atoms derived from isobutylene, or an aryl group having a carbon number of 6-8, alkyl An aryl group or an arylalkyl group is preferable. Examples of these groups include isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), and propylene trimer. Branched nonyl groups derived from the body (including all branched isomers), branched dodecyl groups derived from the propylene tetramer (including all branched isomers), 5 quantities of propylene Branched pentadecyl groups derived from the body (including all branched isomers), branched octadecyl groups derived from the propylene hexamer (including all branched isomers), sec Branched octyl group derived from butyl group, tert-butyl group, 1-butene dimer (including all branched isomers), branched octyl group derived from isobutylene dimer (all ), Branched dodecyl groups derived from 1-butene trimer (including all branched isomers), branched dodecyl groups derived from isobutylene trimer (Including all branched isomers), branched hexadecyl group derived from 1-butene tetramer (including all branched isomers), branched derived from isobutylene tetramer Alkyl groups such as hexadecyl group (including all branched isomers); phenyl group, tolyl group (including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (all (Including structural isomers) Groups; arylalkyl groups such as benzyl group and phenylethyl group (including all isomers).

Furthermore, R ³ and R ⁴ in the general formula (2) are each a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene, from the viewpoint of improving lubricity. Are more preferable, and a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene is particularly preferable.

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

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited. Specifically, specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is used as a solvent. Examples thereof include paraffinic mineral oil, naphthenic mineral oil, and the like, which are refined by appropriately combining purification treatments such as deblocking, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. In addition, as the elemental sulfur, any form such as a lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled in a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in the sulfur content in the sulfide mineral oil concerning this invention, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0. 5% by mass.

  Preferable examples of the zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate and the molybdenum dithiocarbamate include compounds represented by the following general formulas (3) to (6), respectively.

Wherein ^{(3) ~ (6),} R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R ¹⁸ , R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ¹ and X ² each represent an oxygen atom or a sulfur atom.

Here, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ Specific examples of the hydrocarbon group represented by: methyl group, ethyl group, propyl group (including all branched isomers), butyl group (including all branched isomers), pentyl group (including Including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers), nonyl Groups (including all branched isomers), decyl groups (including all branched isomers), undecyl groups (including all branched isomers), dodecyl groups (including all branched isomers) , Tridecyl group (including all branched isomers), tetradecyl group (all ), Pentadecyl group (including all branched isomers), hexadecyl group (including all branched isomers), heptadecyl group (including all branched isomers), octadecyl group (Including all branched isomers), nonadecyl group (including all branched isomers), icosyl group (including all branched isomers), heicosyl group (including all branched isomers), Alkyl groups such as docosyl group (including all branched isomers), tricosyl group (including all branched isomers), tetracosyl group (including all branched isomers); cyclopentyl group, cyclohexyl group, cyclo Cycloalkyl groups such as heptyl group; methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethylcyclopent Group (including all substituted isomers), propylcyclopentyl group (including all branched and substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (all Substituted isomers), butylcyclopentyl group (all branched isomers, including substituted isomers), methylpropylcyclopentyl group (including all branched isomers, substituted isomers), diethylcyclopentyl group (all Substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (Including all substituted isomers), propylcyclohexyl groups (all branched isomers) , Including substituted isomers), methylethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), butylcyclohexyl group (all branched isomers, substituted isomers) Including), methylpropylcyclohexyl group (including all branched isomers and substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers), methyl Cycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (all branched isomers) Isomers, including substituted isomers), methylethylcycloheptyl group (including all substituted isomers) Trimethylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (including all branched isomers, including substituted isomers), methylpropylcycloheptyl group (including all branched isomers, substituted isomers) Alkylcycloalkyl groups such as diethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers); aryl groups such as phenyl group and naphthyl group; tolyl group (Including all substituted isomers), xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (all branched isomers, substituted isomers) ), Methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers), Ruphenyl group (including all branched and substituted isomers), methylpropylphenyl group (including all branched and substituted isomers), diethylphenyl group (including all substituted isomers), dimethyl Ethylphenyl group (including all substituted isomers), pentylphenyl group (including all branched isomers, including substituted isomers), hexylphenyl group (including all branched isomers, including substituted isomers), heptyl Phenyl group (including all branched isomers and substituted isomers), octylphenyl group (including all branched isomers and substituted isomers), nonylphenyl group (all branched isomers and substituted isomers) ), Decylphenyl group (including all branched and substituted isomers), undecylphenyl group (including all branched and substituted isomers), dodecylphenyl group (all Branched isomers, including substituted isomers), tridecylphenyl group (including all branched isomers and substituted isomers), tetradecylphenyl group (including all branched isomers and substituted isomers) , Pentadecylphenyl group (all branched isomers, including substituted isomers), hexadecylphenyl group (including all branched isomers, substituted isomers), heptadecylphenyl group (all branched isomers) Alkylaryl groups such as octadecylphenyl group (including all branched isomers and substituted isomers); benzyl group, phenethyl group, phenylpropyl group (including all branched isomers) And arylalkyl groups such as phenylbutyl group (including all branched isomers).

  In the present invention, among the above sulfur compounds, it is preferable to use at least one selected from the group consisting of dihydrocarbyl polysulfide and sulfurized ester because the effect of improving lubricity can be obtained at a higher level.

  Specific examples of the phosphorus compound used as the lubricity improver include, for example, phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters, and phosphors. Examples include thionate and metal salts of phosphorus compounds represented by the following general formula (7) or (8). Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof.

［式（７）中、Ｘ^３、Ｘ^４及びＸ^５は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を表し、Ｘ^３、Ｘ^４又はＸ^５の少なくとも２つは酸素原子であり、Ｒ^２１、Ｒ^２２、及びＲ^２３は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を表す］

[In Formula (7), X ³ , X ⁴ and X ⁵ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least two of X ³ , X ⁴ or X ⁵ are oxygen atoms. , R ²¹ , R ²² , and R ²³ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms]

［式（８）中、Ｘ^６、Ｘ^７、Ｘ^８及びＸ^９は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を表し、Ｘ^６、Ｘ^７、Ｘ^８又はＸ^９の少なくとも３つは酸素原子であり、Ｒ^２４、Ｒ^２５及びＲ^２６は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を表す。］

[In the formula (8), X ⁶ , X ⁷ , X ⁸ and X ⁹ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least 3 of X ⁶ , X ⁷ , X ⁸ or X ⁹ One is an oxygen atom, and R ²⁴ , R ²⁵ and R ²⁶ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

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

Moreover, regarding the metal salt of the phosphorus compound represented by the general formula (7) or (8), as the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{21 to} R ²⁶ in the formula, specifically, Includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

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

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

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

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

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

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{21 to} R ²⁶ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 3 carbon atoms. An alkyl group having 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

R ²¹ , R ²² and R ²³ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group, and among R ²¹ , R ²² and R ²³ , 1 to 3 are the above hydrocarbon groups. It is preferable that 1 to 2 is the above hydrocarbon group, and more preferably 2 is the above hydrocarbon group.

R ²⁴ , R ²⁵ and R ²⁶ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group. Among R ²⁴ , R ²⁵ and R ²⁶ , 1 to 3 are the above hydrocarbons. It is preferably a group, 1 to 2 are more preferably the hydrocarbon group, and 2 are more preferably the hydrocarbon group.

In the general formula (7) phosphorus compounds represented by, at least two of X ³ to X ⁵ is required to be an oxygen atom, that all X ³ to X ⁵ is an oxygen atom preferable.

In the phosphorus compound represented by the general formula (8), at least three of X ^{6 to} X ⁹ are required to be oxygen atoms, but all of X ^{6 to} X ⁹ are oxygen atoms. It is preferable.

  Examples of the phosphorus compound represented by the general formula (7) include phosphorous acid and monothiophosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms and monothiophosphorous acid mono Ester; Phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester; Phosphorous acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid Acid triesters; and mixtures thereof. Among these, phosphorous acid monoester and phosphorous acid diester are preferable, and phosphorous acid diester is more preferable.

  Examples of the phosphorus compound represented by the general formula (8) include phosphoric acid and monothiophosphoric acid; phosphoric acid monoester and monothiophosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; And phosphoric acid diesters and monothiophosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; phosphoric acid triesters and monothiophosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. It is done. Among these, phosphoric acid monoester and phosphoric acid diester are preferable, and phosphoric acid diester is more preferable.

  Examples of the metal salt of the phosphorus compound represented by the general formula (7) or (8) include a salt obtained by neutralizing part or all of the acidic hydrogen of the phosphorus compound with a metal base. Examples of such metal bases include metal oxides, metal hydroxides, metal carbonates, metal chlorides and the like. Specific examples of the metal include alkali metals such as lithium, sodium, potassium, cesium, and calcium. And alkaline earth metals such as magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  The metal salt of the phosphorus compound has a different structure depending on the valence of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid diester ( When 2 mol of 1 OH group is reacted, a compound having a structure represented by the following formula (9) is considered to be obtained as a main component, but it is also considered that polymerized molecules exist.

  In addition, for example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (two OH groups) are reacted, a compound having a structure represented by the following formula (10) is considered to be obtained as a main component. Polymerized molecules are also thought to exist.

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

  In the present invention, among the above phosphorous compounds, phosphoric acid esters, acidic phosphoric acid esters, and amine salts of acidic phosphoric acid esters are preferred because higher lubricity improvement effects can be obtained.

  Particularly preferred examples of the compound containing phosphorus and / or sulfur used as a lubricity improver include tricresyl phosphate, trilauryl phosphate, trilauryl phosphite, trioleyl phosphite, dilauryl phosphite. , Dilauryl hydrogen phosphite, lauric phosphate, sulfurized oil, sulfurized ester, diphenyl disulfide, dibenzyl disulfide, didodecyl disulfide, di-tert-nonyl polysulfide, trilauryl thiophosphate, trilauryl trithiophosphite, two Examples include molybdenum sulfide, molybdenum dithiophosphate, zinc dithiophosphate, molybdenum dithiocarbamate, and zinc dithiocarbamate.

  The metalworking oil composition of the present invention may contain only one of a sulfur compound and a phosphorus compound as a lubricity improver, or may contain both a sulfur compound and a phosphorus compound. Good. From the point that the effect of improving lubricity is further enhanced, it is preferable to contain a phosphorus compound or both a sulfur compound and a phosphorus compound, and more preferably to contain both a sulfur compound and a phosphorus compound.

  When the metalworking oil composition of the present invention contains a compound containing phosphorus and / or sulfur as constituent elements, the content of the compound containing phosphorus and / or sulfur as constituent elements is arbitrary, but the point of improving lubricity Therefore, it is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more, based on the total amount of the composition. From the viewpoint of preventing abnormal wear, the content is preferably 15% by mass or less, more preferably 10% by mass or less, and preferably 7% by mass or less, based on the total amount of the composition. Even more preferred. In addition, content here means the content, when it uses individually 1 type of the compound containing phosphorus and / or sulfur as a structural element, and when using 2 or more types in combination, total content Means quantity.

  In the metalworking oil composition of the present invention, as a lubricity improver, one of an ester, an alcohol, a carboxylic acid, and a compound containing phosphorus and / or sulfur as a constituent element may be used alone. You may combine 2 or more types.

  The metalworking oil composition of the present invention may be composed only of the above-described lubricating base oil and a lubricity improver, but in order to further improve its excellent effect, oxidation is performed as necessary. An inhibitor, a rust inhibitor, a corrosion inhibitor, an antifoaming agent, etc. may be added alone or in combination of two or more.

  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 can.

  Examples of the corrosion inhibitor include benzotriazole.

  Examples of antifoaming agents include silicone-based ones.

  The total content of these additives is usually 15% by mass or less, preferably 10% by mass or less (both based on the total amount of the composition).

  Moreover, the metalworking oil composition of the present invention may further contain water. In this case, the metalworking oil composition of the present invention is an emulsified state in which water is a continuous layer and the oil component is finely dispersed in the continuous layer to form an emulsion; a solubilized state in which water is dissolved in the oil component Or may be used in any suspension state in which water and an oil component are mixed by vigorous stirring.

  When water is contained in the metalworking oil composition of the present invention, tap water, industrial water, ion-exchanged water, distilled water, or the like can be used as water, regardless of whether it is hard water or soft water.

Kinematic viscosity metalworking oil composition of the present invention is not particularly limited, in general, it is preferable that the kinematic viscosity at 40 ° C. is in the range of 1~150mm ² / s, a range of 2 to 100 mm ² / s It is more preferable that In addition, when the kinematic viscosity at 40 ° C. of the metalworking oil composition is less than 1 mm ² / s, the workability tends to be insufficient. Further, when the kinematic viscosity exceeds 150 mm ² / s, it is difficult for the oil component to be removed from the workpiece in the oil component removing step provided at the subsequent stage of the processing step.

  The metalworking oil composition of the present invention having the above configuration can obtain excellent workability without increasing the viscosity or increasing the amount of additives, and can maintain the workability at a high level over a long period of time. Therefore, it can be suitably used for various metal processing. Examples of metal processing in which the metalworking oil composition of the present invention is used include drawing, ironing, drawing, pressing, forging (including hot forging), cutting / grinding, rolling (hot Including cold rolling and cold rolling). In addition, the material of the workpiece used for these metal processing is not particularly limited, for example, iron, stainless steel, aluminum or an alloy thereof, nickel or an alloy thereof, chromium or an alloy thereof, copper or an alloy thereof, zinc or an alloy thereof. , Titanium or an alloy thereof.

  The metalworking oil composition of the present invention can be used for any of the above-mentioned metalworking, but depending on the type of metalworking, the kinematic viscosity of the lubricating base oil in the metalworking oil composition of the present invention. In addition, it is preferable to appropriately select the type and combination of the lubricity improvers.

For example, when the metalworking oil composition of the present invention is used for drawing or pressing, the lubricating base oil according to the present invention has a kinematic viscosity at 40 ° C. of 20 to 150 mm ² / s. preferable. Moreover, in this case, as the lubricity improver, butyl stearate, alcohol having 10 to 18 carbon atoms (which may be linear or branched, and either saturated or unsaturated) It is preferable to use at least one selected from oleic acid, sulfurized esters, sulfurized fats and oils, zinc dithiophosphate and tricresyl phosphate, and any of the following (A-1) to (A-8) It is particularly preferred.
(A-1) Combination of butyl stearate, sulfide ester and tricresyl phosphate (A-2) Combination of oleic acid, sulfide ester and tricresyl phosphate (A-3) Butyl stearate, lauryl alcohol and olein Combination of acid, sulfurized ester and tricresyl phosphate (A-4) Combination of sulfurized ester and tricresyl phosphate (A-5) Combination of sulfurized ester and zinc dithiophosphate (A-6) Sulfurized oil and fat and dithiophosphorus Combination with zinc acid (A-7) Zinc dithiophosphate (A-8) Sulfurized ester.

Moreover, when the metalworking oil composition of this invention is used for a rolling process, it is preferable that the kinematic viscosity in 40 degreeC of the lubricating base oil concerning this invention is 4-20 mm < ² > / s. Further, in this case, as the lubricity improver, butyl stearate, butyl palmitate, dibutyl adipate, dioctyl adipate, dinonyl adipate, didecyl adipate, oleic acid, alcohol having 10 to 18 carbon atoms (linear form) Or at least one selected from the group consisting of saturated and unsaturated) and tricresyl phosphate, and the following (B-1) It is particularly preferred that any one of (B-7).
(B-1) Combination of butyl stearate, lauryl alcohol, sulfurized ester and tricresyl phosphate (B-2) Combination of butyl stearate and lauryl alcohol (B-3) Combination of sulfurized ester and tricresyl phosphate Combination (B-4) Combination of butyl stearate, lauryl alcohol and oleic acid (B-5) Combination of butyl stearate, adipic acid diester and lauryl alcohol (B-6) Combination of adipic acid diester and lauryl alcohol (B-7) A combination of adipic acid diester, lauryl alcohol and oleic acid.

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

[Manufacture of lubricating base oil]
(Base oils 1-3)
The fraction separated by distillation under reduced pressure in the step of refining the solvent refined base oil was subjected to hydrogenation after solvent extraction with furfural, and then dewaxed with a methyl ethyl ketone-toluene mixed solvent. The wax removed during the solvent dewaxing (hereinafter referred to as “WAX1”) was used as a raw material for the lubricating base oil. Table 1 shows the properties of WAX1.

Next, in the presence of a hydrocracking catalyst, WAX1 was hydrocracked under the conditions of a hydrogen partial pressure of 5 MPa, an average reaction temperature of 340 ° C., and LHSV 0.8 hr ⁻¹ . As the hydrocracking catalyst, a catalyst in which nickel and molybdenum were supported on an amorphous silica / alumina carrier was used in a sulfurized state.

  Next, the cracked product obtained by the above hydrocracking was distilled under reduced pressure to obtain a 20% by volume lubricating oil fraction with respect to the raw material oil. For this lubricating oil fraction, solvent dewaxing was performed using a methyl ethyl ketone-toluene mixed solvent at a solvent / oil ratio of 2 times and a filtration temperature of -30 ° C. , "Base oil 1", "Base oil 2" and "Base oil 3").

(Base oil 4, 5)
700 g of zeolite and 300 g of an alumina binder were mixed and kneaded and molded into a cylindrical shape having a diameter of 1/16 inch (about 1.6 mm) and a height of 8 mm. The obtained molded body was fired at 480 ° C. for 2 hours to obtain a carrier. By impregnating this carrier with an aqueous solution of dichlorotetraamineplatinum (II) in an amount of 1.0% by mass of the carrier in terms of platinum, drying at 125 ° C. for 2 hours, and baking at 380 ° C. for 1 hour, The desired catalyst was obtained.

Next, the obtained catalyst was charged into a fixed bed flow reactor, and hydrocracking / hydroisomerization of feedstock containing paraffinic hydrocarbons was performed using this reactor. In this step, FT wax (hereinafter referred to as “WAX2”) having a paraffin content of 95% by mass and having a carbon number distribution of 20 to 80 was used as the raw material oil. Table 2 shows the properties of WAX2. The hydrocracking conditions were a hydrogen pressure of 3.5 MPa, a reaction temperature of 340 ° C., LHSV 1.5 h ^−1, and a fraction (decomposition product) having a boiling point of 370 ° C. or lower with respect to the raw material was 25 mass% (decomposition rate 25 %) Was obtained.

  Next, a lubricating oil fraction was obtained by distillation under reduced pressure of the cracked / isomerized product oil obtained in the hydrocracking / hydroisomerization step. For this lubricating oil fraction, solvent dewaxing was performed using a methyl ethyl ketone-toluene mixed solvent at a solvent / oil ratio of 3 times and a filtration temperature of -30 ° C. , "Base oil 4" and "base oil 5").

(Base oil 6, 7)
The fraction separated by distillation under reduced pressure in the step of refining the solvent refined base oil was subjected to hydrogenation after solvent extraction with furfural, and then dewaxed with a methyl ethyl ketone-toluene mixed solvent. A wax obtained by further deoiling the slack wax removed during the solvent dewaxing (hereinafter referred to as “WAX3”) was used as a raw material for the lubricant base oil. Table 3 shows the properties of WAX3.

Next, WAX3 was hydrocracked in the presence of a hydrocracking catalyst under the conditions of a hydrogen partial pressure of 5.5 MPa, an average reaction temperature of 340 ° C., and LHSV 0.8 hr ⁻¹ . As the hydrocracking catalyst, a catalyst in which nickel and molybdenum were supported on an amorphous silica / alumina carrier was used in a sulfurized state.

  Next, the cracked product obtained by the above hydrocracking was distilled under reduced pressure to obtain a 20% by volume lubricating oil fraction with respect to the raw material oil. For this lubricating oil fraction, solvent dewaxing was performed using a methyl ethyl ketone-toluene mixed solvent at a solvent / oil ratio of 2 times and a filtration temperature of -30 ° C. , “Base oil 6” and “base oil 7”).

  Various properties and performance evaluation test results of the base oils 1 to 7 are shown in Tables 4 to 5. In addition, Table 5 shows various properties and performance evaluation test results for base oils 8 and 9, which are conventional high viscosity index base oils.

[Examples 1-7, Comparative Examples 1-4]
In Examples 1-7, the metalworking oil composition which has a composition shown in Table 6 was prepared using the base oils 1, 4, 6 shown in Tables 4-5, and the additive shown below, respectively. Moreover, in Comparative Examples 1-4, the metalworking oil composition shown in Table 7 was prepared using the base oil 8 shown in Table 5, or the base oil 10 shown below, and the additive shown below, respectively. Tables 6 to 7 also show the kinematic viscosities of each metalworking oil composition at 40 ° C. In addition, content of the additive shown to Tables 6-7 is content based on the composition whole quantity.
(Base oil)
Base oil 10: paraffinic mineral oil (kinematic viscosity at 40 ° C .: 49.7 mm ² / s, saturated component: 91.5% by mass, ratio of cyclic saturated component to saturated component: 49.8% by mass)
(Additive)
Additive 1: butyl stearate additive 2: lauryl alcohol additive 3: oleic acid additive 4: tricresyl phosphate additive 5: sulfurized ester (inactive type).

  Next, the following evaluation tests were performed on the metalworking oil compositions of Examples 1 to 7 and Comparative Examples 1 to 4.

[Drawing test]
When each of the metalworking oil compositions of Examples 1 to 7 and Comparative Examples 1 to 4 is used to mold an aluminum disk (JIS A 5182, diameter 100 mm, thickness 0.4 mm) into a bottomed container, The maximum punching force required when the force was 1000 kg was measured. The obtained results are shown in Tables 6-7. In Table 5, the smaller the maximum drawing force, the better the workability.

[Oil removal test (1)]
On one side of an aluminum disk (JIS A 5182, diameter 100 mm, thickness 0.4 mm), each of the metalworking oil compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was 3 g / m ^2. It apply | coated using the spray and left still at room temperature for 6 hours. Thereafter, the disc was immersed in a degreasing agent containing a nonionic surfactant for 1 minute, and the removed disc was washed with running water for 30 seconds. Immediately after such water washing, the disk is held so that the radial direction is vertical, the water wetted area after 20 seconds is measured, and the water wetted area is 90% or more of the coated surface area A, less than 90% Was rated B. The obtained results are shown in Tables 6-7. In addition, it means that the thing with a large water-wetting area (namely, the thing of evaluation A) is excellent in oil removal property.

[Examples 8 to 14, Comparative Examples 5 to 8]
In Examples 8 to 14, metalworking oil compositions having the compositions shown in Table 8 were prepared using base oils 2, 5, and 7 shown in Tables 4 to 5 and additives shown below. Moreover, in Comparative Examples 5-8, the metalworking oil composition shown in Table 9 was prepared using the base oil 9 shown in Table 5, or the base oil 11 shown below, and the additive shown below, respectively. Tables 8 to 9 also show the kinematic viscosities of each metalworking oil composition at 40 ° C. In addition, content of the additive shown to Tables 8-9 is content based on the composition whole quantity.
(Base oil)
Base oil 9: paraffinic mineral oil (kinematic viscosity at 40 ° C .: 19.3 mm ² / s, saturated content: 99.1% by mass, ratio of cyclic saturated component to saturated component: 45.9% by mass)
(Additive)
Additive 1: butyl stearate additive 2: lauryl alcohol additive 4: tricresyl phosphate additive 5: sulfurized ester (inactive type).

  Next, the following evaluation tests were performed on the metalworking oil compositions of Examples 8 to 14 and Comparative Examples 5 to 8.

[Rolling processing test]
When rolling a stainless steel rolled material (SUS304, length 100 mm, width 50 mm, thickness 0.25 mm) using each of the metal working oil compositions of Examples 8 to 14 and Comparative Examples 5 to 8, the rolling speed The rolling load required at 250 m / min and a rolling reduction of 35% was measured. The obtained results are shown in Tables 8-9. In Table 5, it means that it is excellent in workability, so that rolling load is small.

[Oil removal test (2)]
3 g / m ² of each of the metalworking oil compositions of Examples 8-14 and Comparative Examples 5-8 on one surface of a stainless steel rolled material (SUS304, length 100 mm, width 50 mm, thickness 0.25 mm). It apply | coated using the spray so that it might become, and left still at room temperature for 6 hours. Next, the rolled material was immersed in n-hexane for 5 seconds, and the taken-out rolled material was dried. Thereafter, the material to be rolled was heated from room temperature to 450 ° C. over 3 hours, held at the same temperature for 1 hour, and then cooled to room temperature over 2 hours (thermal degreasing). The area of the discolored portion of the surface of the material to be rolled after thermal degreasing was measured, and the discolored area was evaluated as A when the discolored area was 95% or more of the area of the coated surface, and B when it was less than 95%. The obtained results are shown in Tables 8-9. In addition, the thing with a large discoloration area (namely, the thing of evaluation A) means that it is excellent in oil removal property.

[Examples 15 to 24, Comparative Examples 9 to 11]
In Examples 15-24, the metalworking oil composition (cutting oil) which has the composition shown in Tables 10-11 using the base oils 3, 5, 7 shown in Tables 4-5, and the additive shown below, respectively. Composition) was prepared. Moreover, in Comparative Examples 9-11, the metalworking oil composition shown in Table 11 was prepared using the base oil 9 shown in Table 5, and the additive shown below, respectively. Tables 10 to 11 also show the kinematic viscosities of each metalworking oil composition at 40 ° C. In addition, in the column of the composition of Tables 10-11, each content of base oil 3, 5, 7, 9 and additive 6-13 is content based on the composition whole quantity.
(Additive)
Additive 6: Active sulfurized ester (sulfur content: 17.5% by mass)
Additive 7: Di-t-dodecyl polysulfide (sulfur content: 32% by mass)
Additive 8: Zinc dithiophosphate compound (sulfur content: 20% by mass, zinc content: 10% by mass, phosphorus content: 9% by mass)
Additive 9: Overbased calcium sulfonate (base number: 400 mgKOH / g)
Additive 10: Ethylene-propylene copolymer (kinematic viscosity at 100 ° C .: 1200 mm ² / s)
Additive 11: Tricresyl phosphate additive 12: High oleic vegetable oil (iodine value: 95, proportion of oleic acid in constituent carboxylic acids: 65% by mass)
Additive 13: n-dodecanol.

  Next, the following evaluation tests were performed on the metalworking oil compositions of Examples 15 to 24 and Comparative Examples 9 to 11.

[Tapping test]
Using the metalworking oil compositions of Examples 15 to 24 and Comparative Examples 9 to 11, a tapping test was performed by a normal oil supply method. Specifically, each metalworking oil composition and comparative standard oil (DIDA: diisodecyl adipate) were alternately used to perform a tapping test under the following conditions, and the tapping energy in each case was measured.
Tapping conditions Tool: Nut tap M8 (P = 1.25mm)
Pilot hole diameter: φ7.2mm
Workpiece: AC8A (t = 10mm)
Cutting speed: 9.0 m / min Oil supply system The metal processing oil composition and DIDA were directly supplied to the processing site under conditions of about 6 mL / min for processing.

Next, tapping energy efficiency (%) was calculated according to the following formula using the obtained tapping energy measurement value. The obtained result is shown to Tables 10-11. In the table, the higher the value of tapping energy efficiency, the higher the lubricity.
Tapping energy efficiency (%) = (Tapping energy when DIDA is used) / (Tapping energy when oil composition is used)

[Oil take-out test]
SPCC steel plates (60 mm × 80 mm) were immersed in the metal working oil compositions of Examples 9 to 15 and Comparative Examples 9 to 11 and held for 1 minute. Then, the SPCC steel plate was taken out and hung vertically for 5 minutes to drain oil, and the adhesion amount (oil take-out amount) of the metalworking oil composition was measured. The obtained result is shown to Tables 10-11.

Claims (1)

Lubricating oil fractions obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation can be subjected to solvent degreasing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing or clay treatment. It is at least one lubricating base oil selected from paraffinic mineral oil, normal paraffinic base oil and isoparaffinic base oil, which are refined by combining one of these refining treatments alone or in combination of two or more. ,% _{C A} of 2 or _{less,% C} P /% C _N is 6 or more 35 or less, and the lubricating oil base oil is an iodine value of 2.5 or less,
A metalworking oil composition comprising: an ester, an alcohol, a carboxylic acid, and at least one lubricity improver selected from compounds containing phosphorus and / or sulfur as constituent elements.