JP5265087B2 - Rust prevention oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a corrosion preventive oil composition which is sufficiently high in adaptability to an organic material, is excellent in handling quality, and can sufficiently prevent the occurrence of rust in a metallic member. <P>SOLUTION: The corrosion preventive oil composition containing a hydrocarbon oil which is 0.7 to 0.8 g/cm<SP>3</SP>in density at 15&deg;C, 10 to 90% in n-paraffin component, 0 to 3% in aromatic component, and 0 to 20% in naphthene is provided. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to rust prevention oil, and more particularly to rust prevention oil useful when used for metal members such as steel plates and bearings.

  Conventionally, in the field of metal members such as steel plates and bearings, rust prevention oil is usually applied to the manufactured member in order to prevent the occurrence of rust.

  As rust prevention oil, it is used only for preventing the occurrence of rust, as well as a cleaning and rust preventive oil having a cleaning action, and also has an action of preventing the occurrence of rust in intermediate products and a lubricating action in the subsequent processing steps. Multifunctional rust preventive oils such as antirust and processing oils are known. In these rust preventive oils, a base oil having a relatively low viscosity or a base oil in which a low viscosity base oil and a high viscosity base oil are mixed is often used for the purpose of improving the handleability.

  By the way, in a device provided with a metal member such as a steel plate or a bearing, since members made of various organic materials are usually used in addition to the metal member, the anticorrosive oil is compatible with the organic material. Although it is also required to be excellent, when a conventional rust preventive oil is used, a member made of an organic material may be deteriorated.

Further, when an organic material is used as a packaging material when shipping a metal member, the packaging material may be deteriorated. In view of such a situation, the present inventors have proposed a rust preventive oil having high compatibility with organic materials (Patent Document 1).
Patent Document 1: Japanese Patent Application Laid-Open No. 2005-290163

  The present invention has been made in view of the above-described problems of the prior art, has sufficiently high compatibility with organic materials, is excellent in handleability, and can sufficiently prevent the occurrence of rust in metal members. It aims to provide a possible rust-preventing oil.

A hydrocarbon oil having a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 10 to 90%, an aromatic content of 0 to 3%, and a naphthene content of 0 to 20%. Containing 85% by mass or more based on the total amount of the composition, the hydrocarbon oil is selected from a Fischer-Tropsch (FT) synthesis step, a hydrocracking step of wax-containing components, and a hydrorefining treatment step of components obtained from these steps There is provided a rust preventive oil composition characterized by being a kerosene oil fraction produced by a production process having at least one process.
The density at 15 ° C. is 0.7 to 0.8 g / cm ³ , the n-paraffin content is 20 to 90%, the aromatic content is 0 to 3%, the naphthene content is 0 to 20%, and the initial boiling point. 140 to 280 ° C, 10% distillation point is 150 to 270 ° C, and the hydrocarbon oil is a Fischer-Tropsch (FT) synthesis step, hydrocracking step of wax-containing components, and these A kerosene fraction produced by a production process having at least one step selected from the hydrorefining treatment step of the component obtained from the step, wherein the hydrocarbon oil is kinematic viscosity at 40 ° C. other than the hydrocarbon oil When used as a solvent-diluted rust-preventing oil by mixing with a base oil having an excess of 6 mm ² / s, the content of the hydrocarbon oil is 5 to 95% by mass based on the total amount of the rust-preventing oil composition. An oil composition is provided.

  It is possible to improve resin compatibility as a rust preventive oil composition.

The rust preventive oil composition of the present invention has a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 10 to 90%, an aromatic content of 0 to 3%, and a naphthene content. A hydrocarbon oil of 0 to 20% is contained in an amount of 85% by mass or more based on the total amount of the composition, and the hydrocarbon oil is obtained from a Fischer-Tropsch (FT) synthesis process, a hydrocracking process of a wax-containing component, and these processes. It is a kerosene oil fraction produced by a production process having at least one process selected from the hydrorefining treatment process of the component to be obtained (hereinafter referred to as the first hydrocarbon oil of the present invention).
The rust preventive oil composition of the present invention has a density at 15 ° C. of 0.7 to 0.8 g / cm ³ , an n-paraffin content of 20 to 90%, an aromatic content of 0 to 3%, and a naphthene. Containing a hydrocarbon oil having a fraction of 0 to 20%, an initial boiling point of 140 to 280 ° C, and a 10% distillation point of 150 to 270 ° C, wherein the hydrocarbon oil is a Fischer-Tropsch (FT) synthesis step, A kerosene oil fraction produced by a production process having at least one process selected from a hydrocracking process of a wax-containing component and a hydrorefining treatment process of a component obtained from these processes, wherein the hydrocarbon oil is When mixed with a base oil having a kinematic viscosity at 40 ° C other than hydrocarbon oil exceeding 6 mm ² / s and used as a solvent-diluted rust prevention oil, the content of the hydrocarbon oil is based on the total amount of the rust prevention oil composition. 5 to 95% by mass Wherein (hereinafter referred to the present invention second hydrocarbon oil). In the following paragraphs, the term “hydrocarbon oil of the present invention” simply refers to “the first or second hydrocarbon oil of the present invention”.
The density (g / cm ³ ) at 15 ° C. of the first or second hydrocarbon oil of the present invention is 0.70 to 0.80, preferably 0.72 to 0.79, more preferably 0.73 to 0. .785. If the density is lower than this, the compatibility with the organic resin material is poor. On the other hand, if it exceeds this range, it is not preferable because the removability of the oil is poor. In addition, the density in this invention means the value measured based on JISK2249.
The n-paraffin content (% by mass) of the hydrocarbon oil of the present invention is 10-90%, preferably 20-80%, more preferably 30-70%. If it is less than this, the compatibility with the organic resin material is inferior, and if it is more, the solubility of the additive is inferior, which is not preferable.
In addition, n-paraffin content here means the value (dilution oil whole quantity reference | standard) measured using GC-FID. In the present invention, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, the column length is 30 m, the carrier gas flow rate is 1. An n-paraffin-containing standard sample was used under the conditions of 0 mL / min, split ratio 1:79, sample injection temperature 360 ° C., column temperature rising condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C. The n-paraffin content (based on the total amount of diluted oil) identified and quantified is shown, but the measurement conditions are not limited as long as equivalent results are obtained.

The content (volume%) of the aromatic component of the hydrocarbon oil of the present invention is 0-10%, preferably 0-3%, more preferably 0-2%, still more preferably 0-1%. If the aromatic content is high, odor is also emitted and skin irritation is exhibited, which is also undesirable because it leads to deterioration of the working environment. Further, the compatibility with the organic resin material is inferior, which is not preferable.
The saturated hydrocarbon content (volume%) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 90-100%, more preferably 97-100%, still more preferably 98-100%, most preferably. Is 99-100%.
Although content (volume%) of the unsaturated part of the hydrocarbon oil of this invention is not specifically limited, Preferably it is 0-5%, More preferably, it is 0-3%, More preferably, it is 0-1%.
In addition, the saturated content, the unsaturated content, and the aromatic content referred to here are measured in accordance with the Petroleum Institute method JPI-5S-49-97 “hydrocarbon type test method—high performance liquid chromatograph method”. It means the volume percentage (volume%) (based on the total amount of diluent oil) of the aromatic content measured according to (published by the Japan Petroleum Institute).
The content (volume%) of the aromatic component of the hydrocarbon oil of the present invention is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%. If it is too much, there is an odor and skin irritation is also undesirable. Further, the compatibility with the organic resin material is inferior, which is not preferable.
The naphthene content (volume%) of the hydrocarbon oil of the present invention is 0-20%, preferably 0-10%, more preferably 0-5%. If the naphthene content is high, an odor is generated, which leads to deterioration of the working environment, which is not preferable. Further, the compatibility with the organic resin material is inferior, which is not preferable.
The paraffin content (% by volume) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 80-100%, more preferably 90-100%, still more preferably 95-100%, and most preferably 99-100. %.
Here, the paraffin content and naphthene content are measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”. It means volume percentage (volume%) (based on the total amount of saturation).

The kinematic viscosity (mm ² / s) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0.5-9, more preferably 1.0-5.5, and more preferably 1.2-5. 0. If the kinematic viscosity is lower than this, the rust prevention property may be inferior. On the other hand, if the kinematic viscosity is higher than this range, the removability of the oil may be inferior. The kinematic viscosity in the present invention means a value measured according to JISK2283.
The flash point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 50-200, more preferably 55-150, and still more preferably 58-140. If the flash point is low, the risk of fire may increase, and if it is high, the removability may be poor. In addition, the flash point in the present invention means a value measured by a tag-sealed or pen-scheme-tensile sealed flash point test method in accordance with JIS K2265.
The aniline point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 65-110, more preferably 70-110, still more preferably 75-110. In addition, the aniline point in this invention means the value measured by JISK2256.
The sulfur content (mass ppm) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0-30, more preferably 0-10, still more preferably 0-5, and most preferably 0-1. If there is a lot of sulfur, the odor may get worse. In addition, the sulfur content in this invention means the value measured by JISK2541.

Distillation properties (° C.) of the hydrocarbon oil of the present invention are as follows according to Engler distillation (JIS K2254).
The initial boiling point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 140 to 280, more preferably 150 to 275, still more preferably 160 to 270, and most preferably 165 to 265. . If it is low, the compatibility with the organic resin material may be inferior.
The 10% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 150-270, more preferably 160-285, still more preferably 170-280, and most preferably 180-275. .
The 50% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 170-320, more preferably 180-310, still more preferably 190-300, and particularly preferably 195-290. It is.
The 90% distillation point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 180-390, more preferably 190-370, still more preferably 200-340, particularly preferably 210-330. is there.
The end point (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 190 to 400, more preferably 200 to 380, still more preferably 210 to 350, and most preferably 220 to 340.
The T ₉₀ -T ₁₀ (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 15-160, more preferably 20-150, still more preferably 30-140, and particularly preferably 35-135.
The EP-IBP (° C.) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 35 to 200, more preferably 40 to 190, still more preferably 50 to 180, and particularly preferably 60 to 170.
The smoke point (mm) of the hydrocarbon oil of the present invention is not particularly limited, but is preferably 0-5, more preferably 0-3, and still more preferably 0-1. In addition, the smoke point in this invention means the value measured by JISK2537.

As mentioned above, although the hydrocarbon oil of this invention has been demonstrated, the following 1st aspect is mentioned as a more concrete preferable aspect.
In a preferred first embodiment, the kinematic viscosity (mm ² / s) is preferably 1.4-2.7, more preferably 1.0-5.5, more preferably 1.2-5.0. . On the other hand, if the kinematic viscosity is lower than this, the antirust property is inferior, while if it exceeds this range, the removability of the oil agent is inferior.
In a preferred first embodiment, the initial boiling point (° C.) is preferably 140-260, preferably 150-255, more preferably 160-250, most preferably 165-245. If the initial boiling point is low, the compatibility with the organic resin material may be inferior.
In a preferred first embodiment, the 10% distillation point (° C.) is preferably 150-270, preferably 160-265, more preferably 170-260, most preferably 180-255.
In a preferred first embodiment, the 90% distillation point (° C) is preferably 180-320, preferably 190-310, more preferably 200-300, most preferably 210-290.
In a preferred first embodiment, the end point (° C.) is preferably 190-310, preferably 200-300, more preferably 210-290, most preferably 220-280.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The present invention contains the above-mentioned first or second hydrocarbon oil of the present invention as a solvent base oil, but in addition to this, any of mineral oil, synthetic oil and fats and oils can be used in combination. Although not used, mineral oil or synthetic oil is particularly preferred for combined use. The combination ratio is not particularly limited and can be arbitrarily selected as long as the effects of the present invention are not impaired. However, the content of the first hydrocarbon oil of the present invention is 85% by mass or more based on the total amount of the rust preventive oil composition. It is necessary to be. Further, the content of the base oil other than the first hydrocarbon oil of the present invention is preferably 60% by mass or less, more preferably 50% by mass or less, based on the total amount of the rust prevention oil composition, Most preferably, it is at most mass%.
The base oil other than the second hydrocarbon oil of the present invention to be used in combination is a base oil having a higher viscosity than the hydrocarbon oil of the present invention, more specifically, a base having a kinematic viscosity at 40 ° C. exceeding 6 mm 2 / s. It is preferable to use oil as a solvent-diluted rust preventive oil. When used as such a solvent-diluted rust preventive oil, the content of the second hydrocarbon oil of the present invention needs to be 5 to 95% by mass based on the total amount of the rust preventive oil composition, it is good Mashiku 10 to 90 wt%, and more preferably from 15 to mass 85%. Moreover, it is preferable that content of the base oil whose kinematic viscosity in 40 degreeC other than this invention 2nd hydrocarbon oil exceeds 6 mm2 / s is 5-95 mass% on the basis of rust prevention oil composition whole quantity, It is more preferably 10 to 90% by mass, and most preferably 15 to 85% by mass.

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

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

Further, the rust preventive oil composition of the present invention can contain an oxidized wax salt, carboxylic acid and the like.
The oxidized wax salt will be described below. The oxidized wax salt is at least one selected from an oxidized wax obtained by oxidizing a wax, an alkali metal, an alkaline earth metal (excluding barium) and an amine. And a salt obtained by neutralizing some or all of the acidic groups of the oxidized wax.

  Although it does not restrict | limit especially as an oxidation wax used as a raw material of an oxidation wax salt, For example, the paraffin wax obtained at the time of refinement | purification of a petroleum fraction, microcrystalline wax, petrolatum, polyolefin wax obtained by synthesis, etc. And the like produced by oxidizing the wax.

  When the oxidized wax salt is an alkali metal salt, examples of the alkali metal used as a raw material include sodium and potassium.

  When the oxidized wax salt is an alkaline earth metal salt, examples of the alkaline earth metal used as a raw material include magnesium, calcium, barium and the like.

  When the oxidized wax salt is a heavy metal salt, examples of the heavy metal used as a raw material include zinc and lead.

  In addition, from the viewpoint of safety with respect to the human body and biological system, it is preferable that the oxidized wax salt is not a barium salt or a heavy metal salt.

  When the oxidized wax salt is an amine salt, examples of the amine include monoamines, polyamines, and alkanolamines.

Specific examples of monoamines include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine (including all isomers), dipropylamine (including all isomers), and tripropyl. Amine (including all isomers), monobutylamine (including all isomers), dibutylamine (including all isomers), tributylamine (including all isomers), monopentylamine (all isomers) ), Dipentylamine (including all isomers), tripentylamine (including all isomers), monohexylamine (including all isomers), dihexylamine (including all isomers) , Monoheptylamine (including all isomers), diheptylamine (including all isomers), Nooctylamine (including all isomers), dioctylamine (including all isomers), monononylamine (including all isomers), monodecylamine (including all isomers), monoundecyl (all ), Monododecylamine (including all isomers), monotridecylamine (including all isomers), monotetradecylamine (including all isomers), monopentadecylamine (including all isomers) Including all isomers), monohexadecylamine (including all isomers), monoheptadecylamine (including all isomers), monooctadecylamine (including all isomers), monononadecylamine (Including all isomers), monoicosylamine (including all isomers), monohenicosylamine (including all isomers), monodocosylamine Including all isomers), monotricosylamine (including all isomers), dimethyl (ethyl) amine, dimethyl (propyl) amine (including all isomers), dimethyl (butyl) amine (all isomers) ), Dimethyl (pentyl) amine (including all isomers), dimethyl (hexyl) amine (including all isomers), dimethyl (heptyl) amine (including all isomers), dimethyl (octyl) Amine (including all isomers), dimethyl (nonyl) amine (including all isomers), dimethyl (decyl) amine (including all isomers), dimethyl (undecyl) amine (including all isomers) ), Dimethyl (dodecyl) amine (including all isomers), dimethyl (tridecyl) amine (including all isomers), dimethyl (tetradecyl) amine Min (including all isomers), dimethyl (pentadecyl) amine (including all isomers), dimethyl (hexadecyl) amine (including all isomers), dimethyl (heptadecyl) amine (including all isomers) ), Dimethyl (octadecyl) amine (including all isomers), dimethyl (nonadecyl) amine (including all isomers), dimethyl (icosyl) amine (including all isomers), dimethyl (henicosyl) amine ( Alkylamines such as all isomers), dimethyl (tricosyl) amine (including all isomers);
Monovinylamine, divinylamine, trivinylamine, monopropenylamine (including all isomers), dipropenylamine (including all isomers), tripropenylamine (including all isomers), monobutenylamine (Including all isomers), dibutenylamine (including all isomers), tributenylamine (including all isomers), monopentenylamine (including all isomers), dipentenylamine (all isomers) ), Tripentenylamine (including all isomers), monohexenylamine (including all isomers), dihexenylamine (including all isomers), monoheptenylamine (all isomers) ), Diheptenylamine (including all isomers), monooctenylamine (including all isomers), dioctenylamine (Including all isomers), monononenylamine (including all isomers), monodecenylamine (including all isomers), monoundecenyl (including all isomers), monododecenylamine (Including all isomers), monotridecenylamine (including all isomers), monotetradecenylamine (including all isomers), monopentadecenylamine (including all isomers), Monohexadecenylamine (including all isomers), monoheptadecenylamine (including all isomers), monooctadecenylamine (including all isomers), monononadecenylamine (all isomers) ), Monoicosenylamine (including all isomers), monohenicocenylamine (including all isomers), monodocosenylamine (including all isomers), Trichoderma cell (including all isomers) cycloalkenyl amines alkenyl amines, such as;
Dimethyl (vinyl) amine, dimethyl (propenyl) amine (including all isomers), dimethyl (butenyl) amine (including all isomers), dimethyl (pentenyl) amine (including all isomers), dimethyl ( Hexenyl) amine (including all isomers), dimethyl (heptenyl) amine (including all isomers), dimethyl (octenyl) amine (including all isomers), dimethyl (nonenyl) amine (all isomers) ), Dimethyl (decenyl) amine (including all isomers), dimethyl (undecenyl) amine (including all isomers), dimethyl (dodecenyl) amine (including all isomers), dimethyl (tridecenyl) Amine (including all isomers), dimethyl (tetradecenyl) amine (including all isomers), dimethyl (pen Decenyl) amine (including all isomers), dimethyl (hexadecenyl) amine (including all isomers), dimethyl (heptadecenyl) amine (including all isomers), dimethyl (octadecenyl) amine (all isomers) ), Dimethyl (nonadecenyl) amine (including all isomers), dimethyl (icosenyl) amine (including all isomers), dimethyl (henicosenyl) amine (including all isomers), dimethyl (tricosenyl) Monoamines having alkyl and alkenyl groups such as amines (including all isomers);
Monobenzylamine, (1-phenyltyl) amine, (2-phenylethyl) amine (also known as monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenylethylene) amine (also known as diphenethylamine) Aromatic substituted alkylamines such as
C5-C16 cycloalkylamines such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine;
Monoamines having an alkyl group and a cycloalkyl group, such as dimethyl (cyclopentyl) amine, dimethyl (cyclohexyl) amine, dimethyl (cycloheptyl) amine;
(Methylcyclopentyl) amine (including all substituted isomers), bis (methylcyclopentyl) amine (including all substituted isomers), (dimethylcyclopentyl) amine (including all substituted isomers), bis (dimethylcyclopentyl) ) Amine (including all substituted isomers), (ethylcyclopentyl) amine (including all substituted isomers), bis (ethylcyclopentyl) amine (including all substituted isomers), (methylethylcyclopentyl) amine ( All substituted isomers included), bis (methylethylcyclopentyl) amine (including all substituted isomers), (diethylcyclopentyl) amine (including all substituted isomers), (methylcyclohexyl) amine (all substituted isomers) Isomers), bis (methylcyclohexyl) amine (all substituted isomers) ), (Dimethylcyclohexyl) amine (including all substituted isomers), bis (dimethylcyclohexyl) amine (including all substituted isomers), (ethylcyclohexyl) amine (including all substituted isomers), bis (Ethylcyclohexyl) amine (including all substituted isomers), (Methylethylcyclohexyl) amine (including all substituted isomers), (Diethylcyclohexyl) amine (including all substituted isomers), (Methylcycloheptyl) ) Amine (including all substituted isomers), bis (methylcycloheptyl) amine (including all substituted isomers), (dimethylcycloheptyl) amine (including all substituted isomers), (ethylcycloheptylamine) (Including all substituted isomers), (methylethylcycloheptyl) amine (all substituted isomers) And alkyl cycloalkylamines such as (diethylcycloheptyl) amine (including all substituted isomers), etc. In addition, monoamines herein include monoamines derived from fats and oils (such as beef tallow amines) ) Is also included.

Specific examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine. , Alkylene polyamines such as dibutylene triamine, butylene tetramine, tetrabutylene pentamine, pentabylene hexamine;
N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine (including all isomers), N-butylethylenediamine (including all isomers), N-pentylethylenediamine (including all isomers), N -Hexylethylenediamine (including all isomers), N-heptylethylenediamine (including all isomers), N-octylethylenediamine (including all isomers), N-nonylethylenediamine (including all isomers) N-decylethylenediamine (including all isomers), N-undecyl (including all isomers), N-dodecylethylenediamine (including all isomers), N-tridecylethylenediamine (including all isomers) Including), N-tetradecylethylenediamine (including all isomers), -Pentadecylethylenediamine (including all isomers), N-hexadecylethylenediamine (including all isomers), N-heptadecylethylenediamine (including all isomers), N-octadecylethylenediamine (all isomers) N-nonadecylethylenediamine (including all isomers), N-icosylethylenediamine (including all isomers), N-henicosylethylenediamine (including all isomers), N-doco N-alkylethylenediamines such as silethylenediamine (including all isomers), N-tricosylethylenediamine (including all isomers);
N-vinylethylenediamine, N-propenylethylenediamine (including all isomers), N-butenylethylenediamine (including all isomers), N-pentenylethylenediamine (including all isomers), N-hexenylethylenediamine ( Including all isomers), N-heptenylethylenediamine (including all isomers), N-octenylethylenediamine (including all isomers), N-nonenylethylenediamine (including all isomers), N-decenylethylenediamine (including all isomers), N-undecenyl (including all isomers), N-dodecenylethylenediamine (including all isomers), N-tridecenylethylenediamine (including all isomers) All isomers), N-tetradecenylethylenediamine (including all isomers), N- Ntadecenylethylenediamine (including all isomers), N-hexadecenylethylenediamine (including all isomers), N-heptadecenylethylenediamine (including all isomers), N-octade Cenylethylenediamine (including all isomers), N-nonadecenylethylenediamine (including all isomers), N-icosenylethylenediamine (including all isomers), N-henicocenylethylenediamine N-alkenylethylenediamine such as (including all isomers), N-docosenylethylenediamine (including all isomers), N-tricosenylethylenediamine (including all isomers);
N-alkyldiethylenetriamine, N-alkenyldiethylenetriamine, N-alkyltriethylenetetramine, N-alkenyltriethylenetetramine, N-alkyltetraethylenepentamine, N-alkenyltetraethylenepentamine, N-alkylpentaethylenehexamine, N-alkenyl Pentaethylenehexamine, N-alkylpropylenediamine, N-alkenylpropylenediamine, N-alkyldipropylenetriamine, N-alkenyldipropylenetriamine, N-alkyltripropylenetetramine, N-alkenyltripropylenetetramine, N-alkyltetrapropylenepenta Min, N-alkenyltetrapropylenepentamine, N-alkylpentapropylenehexamine, N-alkenylpentapropylene Hexamine, N-alkylbutylenediamine, N-alkenylbutylenediamine, N-alkyldibutylenetriamine, N-alkenyldibutylenetriamine, N-alkyltributylenetetramine, N-alkenyltributylenetetramine, N-alkyltetrabutylenepentamine, N-alkyl or N-alkenyl alkylene polyamines such as N-alkenyltetrabutylenepentamine, N-alkylpentabylenehexamine, N-alkenylpentabylenehexamine and the like. The polyamine referred to here also includes polyamines derived from fats and oils (such as beef tallow polyamine).

  Further, as the alkanolamine, specifically, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, Tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine (including all isomers), dibutanolamine (including all isomers), tributanolamine (all Isomers), monopentanolamine (including all isomers), dipentanolamine (including all isomers), tripentanolamine (including all isomers), monohexanolamine (all Isomers), di Xanolamine (including all isomers), monoheptanolamine (including all isomers), diheptanolamine (including all isomers), monooctanolamine (including all isomers), Monononanolamine (including all isomers), monodecanolamine (including all isomers), monoundecanolamine (including all isomers), monododecanolamine (including all isomers) ), Monotridecanolamine (including all isomers), monotetradecanolamine (including all isomers), monopentadecanolamine (including all isomers), monohexadecanolamine (including all isomers) All isomers), diethyl monoethanolamine, diethyl monopropanolamine (including all isomers), diethyl monobutanol amine (Including all isomers), diethylmonopentanolamine (including all isomers), dipropylmonoethanolamine (including all isomers), dipropylmonopropanolamine (including all isomers) ), Dipropylmonobutanolamine (including all isomers), dipropylmonopentanolamine (including all isomers), dibutylmonoethanolamine (including all isomers), dibutylmonopropanolamine (all ), Dibutylmonobutanolamine (including all isomers), dibutylmonopentanolamine (including all isomers), monoethyldiethanolamine, monoethyldipropanolamine (including all isomers) ), Monoethyldibutanolamine (including all isomers), monoethyldipenta Nolamine (including all isomers), monopropyldiethanolamine (including all isomers), monopropyldipropanolamine (including all isomers), monopropyldibutanolamine (including all isomers), Monopropyldipentanolamine (including all isomers), monobutyldiethanolamine (including all isomers), monobutyldipropanolamine (including all isomers), monobutyldibutanolamine (all isomers) ), Monobutyldipentanolamine (including all isomers), monocyclohexyl monoethanolamine, monocyclohexyldiethanolamine, monocyclohexylmonopropanolamine (including all isomers), monocyclohexyldipropanolamine ( Includes all isomers ), And the like.

  Among the above-mentioned amines, monoamines are preferable in that they have good stain resistance. Among monoamines, monoamines having alkylamines, alkyl groups and alkenyl groups, monoamines having alkyl groups and cycloalkyl groups, cycloalkylamines and alkyls. Cycloalkylamine is more preferred. An amine having a total carbon number of 3 or more in the amine molecule is preferable in terms of good stain resistance, and an amine having a total carbon number of 5 or more is more preferable.

  In the present invention, as the oxidized wax salt, one of the above alkali metal salts, alkaline earth metal salts, heavy metal salts or amine salts can be used alone or in combination of two or more. From the viewpoint of properties, it is preferably at least one selected from alkali metal salts and alkaline earth metal salts, and more preferably alkaline earth metal salts. Furthermore, among alkaline earth metal salts, calcium salts are particularly preferable from the viewpoints of safety and higher combined effect with carboxylic acid.

  The content of the oxidized wax salt in the rust prevention oil composition of the present invention is not particularly limited, but from the viewpoint of rust prevention properties, it is preferably 0.5% by mass or more, more preferably 1% by mass based on the total amount of the composition. As mentioned above, More preferably, it is 2 mass% or more. The content of the oxidized wax salt is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less, based on the total amount of the composition, from the viewpoint of degreasing and storage stability. is there.

  In addition, as the carboxylic acid contained in the rust preventive oil composition of the present invention, any can be used, but preferably, fatty acid, dicarboxylic acid, hydroxy fatty acid, naphthenic acid, resin acid, oxidized wax, lanolin fatty acid and the like are used. Can be mentioned.

  Although the carbon number of the fatty acid used in the present invention is not particularly limited, it is preferably 6 to 24, more preferably 10 to 22. The fatty acid used in the present invention may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Specific examples of such fatty acids include hexanoic acid (including all isomers), heptanoic acid (including all isomers), octanoic acid (including all isomers), nonanoic acid (all Isomers), decanoic acid (including all isomers), undecanoic acid (including all isomers), dodecanoic acid (including all isomers), tridecanoic acid (including all isomers), Tetradecanoic acid (including all isomers), pentadecanoic acid (including all isomers), hexadecanoic acid (including all isomers), heptadecanoic acid (including all isomers), octadecanoic acid (all isomers) ), Nonadecanoic acid (including all isomers), icosanoic acid (including all isomers), heicosanoic acid (including all isomers), docosanoic acid (including all isomers), tricosane Acid (all isomeric Saturated fatty acids such as tetracosanoic acid (including all isomers); hexenoic acid (including all isomers), heptenoic acid (including all isomers), octenoic acid (including all isomers) ), Nonenoic acid (including all isomers), decenoic acid (including all isomers), undecenoic acid (including all isomers), dodecenoic acid (including all isomers), tridecenoic acid (all ), Tetradecenoic acid (including all isomers), pentadecenoic acid (including all isomers), hexadecenoic acid (including all isomers), heptadecenoic acid (including all isomers) , Octadecenoic acid (including all isomers), nonadecenoic acid (including all isomers), icosenoic acid (including all isomers), henicosenoic acid (including all isomers), docosenoic acid (all Including isomers) And mixtures thereof; (including all isomers) tricosenoic acid, (including all isomers) tetracosenoic acid unsaturated fatty acids such as.

  As the dicarboxylic acid, preferably a dicarboxylic acid having 2 to 40 carbon atoms, more preferably a dicarboxylic acid having 5 to 36 carbon atoms is used. Among these, dimer acid, alkyl or alkenyl succinic acid obtained by dimerizing an unsaturated fatty acid having 6 to 18 carbon atoms is preferably used. Specific examples of the dimer acid include dimer acid of oleic acid. Among alkyl or alkenyl succinic acids, alkenyl succinic acid is preferable, and alkenyl succinic acid having an alkenyl group having 8 to 18 carbon atoms is more preferable.

  As the hydroxy fatty acid, a hydroxy fatty acid having 6 to 24 carbon atoms is preferably used. The hydroxy fatty acid may have one or more hydroxy groups, but those having 1 to 3 hydroxy groups are preferably used. Specific examples of such hydroxy fatty acids include ricinoleic acid and the like.

  Naphthenic acid is a carboxylic acid in petroleum having a —COOH group bonded to a naphthene ring.

  The resin acid refers to an organic acid present in a free state or as an ester in the natural resin.

  The oxidized wax is obtained by oxidizing a wax. The wax used as the raw material is not particularly limited, and specific examples include paraffin wax obtained during refining of petroleum fractions, microcrystalline wax, petratum, and polyolefin wax obtained by synthesis.

  Lanolin fatty acid is a carboxylic acid obtained by purifying (hydrolyzing, etc.) a waxy substance adhering to sheep wool.

  Among these carboxylic acids, dicarboxylic acid is preferable, dimer acid is more preferable, and dimer acid of oleic acid is more preferable from the viewpoint of rust prevention property, degreasing property, and storage stability.

  The content of carboxylic acid in the rust preventive oil composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0, based on the total amount of the composition. 0.05% by mass or more. When the content of carboxylic acid is less than the lower limit, the effect of improving rust prevention due to the addition tends to be insufficient. The carboxylic acid content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.2% by mass or less, based on the total amount of the composition. If the content of carboxylic acid exceeds the upper limit, the solubility in the base oil becomes insufficient, and the storage stability tends to decrease.

  Further, the content ratio of the oxidized wax salt and the carboxylic acid is not particularly limited, but the ratio (mass ratio) of the carboxylic acid / oxidized wax salt is preferably 1/100 to 30/100, and 3/100 to 7 / 100 is more preferable, and 4/100 to 6/100 is still more preferable. When the ratio of carboxylic acid / oxidized wax salt is less than 1/100 or more than 30/100, the effect of improving the rust prevention property, degreasing property and storage stability by the combination of both tends to be insufficient. .

  The rust preventive oil composition of the present invention can further contain various additives shown below as required.

  The rust preventive oil composition of the present invention may further contain a rust preventive additive such as sulfonate, carboxylate, ester, sarcosine type compound, amine, boron compound and the like.

  Preferred examples of the sulfonate include alkali metal sulfonate, alkaline earth metal sulfonate, and amine sulfonate. All sulfonates have sufficiently high safety for the human body and ecosystem, and can be obtained by reacting an alkali metal, alkaline earth metal or amine with sulfonic acid.

  Examples of the alkali metal and alkaline earth metal constituting the sulfonate include the alkali metal and alkaline earth metal exemplified in the description of the alkali metal salt and alkaline earth metal salt of the oxidized wax, respectively. Calcium is preferred.

  Examples of the amine constituting the sulfonate include the amines exemplified in the description of the amine salt of the oxidized wax. Among these, monoamines are preferable in terms of more excellent anti-rust properties. Among monoamines, alkylamines, monoamines having an alkyl group and an alkenyl group, monoamines having an alkyl group and a cycloalkyl group, cycloalkylamines and alkylcycloalkylamines are more preferable. preferable. An amine having a total carbon number of 3 or more in the amine molecule is preferred because it is more excellent in rust prevention, and an amine having a total carbon number of 5 or more is more preferred.

  On the other hand, as the sulfonic acid according to the present invention, a conventionally known sulfonic acid produced by a conventional method can be used. Specifically, from sulfonated alkyl aromatic compounds in the lubricating oil fraction of mineral oil, petroleum sulfonic acids such as mahogany acid produced as a by-product during white oil production, or from alkylbenzene production plants used as raw materials for detergents, etc. Synthesis of sulfonated alkylbenzene having linear or branched alkyl groups or sulfonated alkylnaphthalene such as dinonylnaphthalene obtained as a by-product or alkylating polyolefin with benzene And sulfonic acid. Although there is no restriction | limiting in particular about the molecular weight of these sulfonic acids, Preferably it is 100-1500, More preferably, the thing of 200-700 is used.

Among the above sulfonic acids,
Dialkylnaphthalenesulfonic acid wherein the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14-30;
Two alkyl groups bonded to the benzene ring are each a branched alkyl group having one linear alkyl group or one side chain methyl group, and a dialkylbenzene sulfone having a total carbon number of 14 to 30 of the two alkyl groups An acid; and a monoalkylbenzenesulfonic acid in which the alkyl bonded to the benzene ring has 15 or more carbon atoms,
It is preferable to use at least one selected from the group consisting of

  As described above, the dialkylnaphthalenesulfonic acid preferably used in the present invention has a total number of carbon atoms of two alkyl groups bonded to the naphthalene ring of 14 to 30. When the total number of carbon atoms of the two alkyl groups is less than 14, the demulsibility tends to be insufficient, and when it exceeds 30, the storage stability of the obtained rust preventive oil composition tends to be lowered. Note that each of the two alkyl groups may be linear or branched. Moreover, if the total carbon number of two alkyl groups is 14-30, there will be no restriction | limiting in particular about the carbon number of each alkyl group, However, It is preferable that the carbon number of each alkyl group is 6-18, respectively.

  Further, as described above, the dialkylbenzenesulfonic acid preferably used in the present invention is a branched alkyl group in which two alkyl groups bonded to the benzene ring each have one linear alkyl group or one side chain methyl group. And the total number of carbon atoms of the two alkyl groups is 14-30. In the case of monoalkylbenzenesulfonic acid, it can be suitably used as long as the alkyl group has 15 or more carbon atoms, as will be described later. However, when a monoalkylbenzenesulfonic acid having an alkyl group having less than 15 carbon atoms is used, rust prevention oil is used. The storage stability of the composition tends to decrease. Also, when an alkylbenzene sulfonic acid having 3 or more alkyl groups is used, the storage stability of the rust preventive oil composition tends to decrease. Further, the alkyl group bonded to the benzene ring of the dialkylbenzenesulfonic acid has a branched alkyl group having a branched structure other than the side chain methyl group (for example, a branched alkyl group having a side chain ethyl group, etc.) or two A branched alkyl group having the above branched structure (for example, a branched alkyl group derived from an oligomer of propylene) may adversely affect the human body or ecosystem, and has rust prevention properties. It tends to be insufficient. Furthermore, if the total number of carbon atoms of the two alkyl groups bonded to the benzene ring of the dialkylbenzene sulfonic acid is less than 14, the demulsibility tends to be reduced. The stability tends to decrease. In addition, as long as the total carbon number of two alkyl groups couple | bonded with a benzene ring is 14-30, there will be no limitation in particular about the carbon number of each alkyl group, but carbon number of each alkyl group shall be 6-18, respectively. Is preferred.

  Furthermore, the monoalkylbenzene sulfonic acid preferably used in the present invention has one or more alkyl groups bonded to the benzene ring having 15 or more carbon atoms as described above. When the carbon number of the alkyl group bonded to the benzene ring is less than 15, the storage stability of the obtained rust preventive oil composition tends to be lowered. Further, the alkyl group bonded to the benzene ring may be linear or branched as long as the carbon number is 15 or more.

Specific examples of the sulfonate obtained using the above raw materials include the following. That is,
Alkali metal bases (alkali metal oxides, hydroxides, etc.), alkaline earth metal bases (alkali earth metal oxides, hydroxides, etc.) or amines (ammonia, alkylamines, alkanolamines, etc.) Neutral (normal salt) sulfonates obtained by reacting with sulfonic acids;
A basic sulfonate obtained by heating the neutral (normal salt) sulfonate and an excess of an alkali metal base, an alkaline earth metal base or an amine in the presence of water;
Carbonate overbased (superbasic) sulfonate obtained by reacting the neutral (normal salt) sulfonate with an alkali metal base, alkaline earth metal base or amine in the presence of carbon dioxide;
Reaction of the neutral (normal salt) sulfonate with an alkali metal base, an alkaline earth metal base or amine, and a boric acid compound such as boric acid or boric anhydride, or the carbonate overbasing (superbase) A borate overbased (superbasic) sulfonate obtained by a reaction between a sulfonate and a boric acid compound such as boric acid or boric anhydride, and a mixture thereof.

  In addition, when producing the neutral (normal salt) sulfonate, the same alkali metal, alkaline earth metal or amine chloride as the target sulfonate as a reaction accelerator is added, After preparing a neutral (normal salt) sulfonate of a different alkali metal, alkaline earth metal or amine, the same alkali metal alkaline earth metal or amine chloride as the target sulfonate is added to carry out an exchange reaction. It is also possible to obtain the desired sulfonate. However, chloride ions are likely to remain in the sulfonate obtained by such a method. Therefore, in the present invention, the sulfonate obtained by such a method is not used, or the sulfonate obtained. It is preferable to perform sufficient washing treatment such as washing with water. Specifically, the chlorine concentration in the sulfonate is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, preferably 50 ppm by mass or less, and 25 ppm by mass or less. It is particularly preferred.

Dialkylnaphthalene sulfonates in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30;
Two alkyl groups bonded to the benzene ring are each a branched alkyl group having one linear alkyl group or one side chain methyl group, and a dialkylbenzene sulfone having a total carbon number of 14 to 30 of the two alkyl groups Acid salts; and monoalkylbenzenesulfonates in which the number of carbon atoms of the alkyl bonded to the benzene ring is 15 or more,
It is preferable to use at least one selected from the group consisting of

  In the present invention, among the above, it is more preferable to use one or more selected from neutral, basic and overbased alkali metal sulfonates and alkaline earth metal sulfonates; base number of 0 to 50 mgKOH / G, preferably 10 to 30 mg KOH / g of neutral or near neutral alkali metal sulfonate or alkaline earth metal sulfonate and / or base number of 50 to 500 mg KOH / g, preferably 200 to 400 mg KOH / g (excess) Particular preference is given to using basic alkali metal sulfonates or alkaline earth metal sulfonates. The content of the alkali metal sulfonate or alkaline earth metal sulfonate having a base number of 0 to 50 mgKOH / g is preferably 0.1 to 15% by mass, more preferably 2 to 12% by mass based on the total amount of the composition. is there. In addition, the mass ratio of the alkali metal sulfonate or alkaline earth metal sulfonate having a base number of 0 to 50 mgKOH / g to the alkali metal sulfonate or alkaline earth metal sulfonate having a base number of 50 to 500 mgKOH / g (the base number is 0). -50 mg KOH / g alkali metal sulfonate or alkaline earth metal sulfonate / base number 50-500 mg KOH / g alkali metal sulfonate or alkaline earth metal sulfonate) is preferably 0.1-30, more preferably 1-20. Especially preferably, it is 1.5-15. Here, examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include barium, calcium and magnesium. Calcium and magnesium are preferable, and calcium is particularly preferable. In addition, the base number as used herein refers to a JIS K 2501 “Petroleum Products and Lubricating Oils—Neutralization Number Test Method” in a state containing 30 to 70% by mass of a diluent such as a lubricating base oil. Means the base number measured by the hydrochloric acid method in accordance with

  Examples of the carboxylate include alkali metal salts, alkaline earth metal salts, and amine salts of carboxylic acids. Examples of the alkali metal, alkaline earth metal and amine constituting the carboxylate include the alkali metal, alkaline earth metal and amine exemplified in the description of the oxidized wax salt. Barium salt may be insufficiently safe for the human body and ecosystem.

  Carboxylic acid salts can be used in combination with other rust inhibitors, but when an oxidized wax salt and a lanolin fatty acid salt are used in combination with a sulfonic acid sodium salt, sodium salts are used as the oxidized wax salt and the lanolin fatty acid salt, respectively. It is preferable.

  Examples of the esters include partial esters of polyhydric alcohols, esterified oxidized waxes, esterified lanolin fatty acids, alkyl or alkenyl succinic acid esters, and the like.

  The partial ester of a polyhydric alcohol is an ester in which at least one of the hydroxyl groups in the polyhydric alcohol is not esterified and remains as a hydroxyl group, and any polyhydric alcohol as a raw material thereof can be used. Can be used, but the number of hydroxyl groups in the molecule is preferably 2 to 10 (more preferably 3 to 6) and the number of carbon atoms is 2 to 20 (more preferably 3 to 10). Alcohol is preferably used. Among these polyhydric alcohols, it is preferable to use at least one polyhydric alcohol selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitan, and it is more preferable to use pentaerythritol.

  On the other hand, as the carboxylic acid constituting the partial ester, an arbitrary one is used, and the carbon number of the carboxylic acid is preferably 2 to 30, more preferably 6 to 24, and still more preferably 10 to 22. The carboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, and may be a linear carboxylic acid or a branched carboxylic acid. Such fatty acids include acetic acid, propionic acid, butanoic acid (including all isomers), pentanoic acid (including all isomers), hexanoic acid (including all isomers), heptanoic acid (all Isomers), octanoic acid (including all isomers), nonanoic acid (including all isomers), decanoic acid (including all isomers), undecanoic acid (including all isomers), Dodecanoic acid (including all isomers), tridecanoic acid (including all isomers), tetradecanoic acid (including all isomers), pentadecanoic acid (including all isomers), hexadecanoic acid (all isomers) ), Heptadecanoic acid (including all isomers), octadecanoic acid (including all isomers), nonadecanoic acid (including all isomers), icosanoic acid (including all isomers), heicossan Acid (all ), Docosanoic acid (including all isomers), tricosanoic acid (including all isomers), tetracosanoic acid (including all isomers), pentacosanoic acid (including all isomers), Hexacosanoic acid (including all isomers), heptacosanoic acid (including all isomers), octacosanoic acid (including all isomers), nonacosanoic acid (including all isomers), triacontanoic acid (all Saturated fatty acids (including isomers) (these saturated fatty acids may be linear or branched); propenoic acid, butenoic acid (including all isomers), heptenoic acid, hexenoic acid, heptenoic acid (all Isomers), octenoic acid (including all isomers), nonenoic acid (including all isomers), decenoic acid (including all isomers), undecenoic acid (including all isomers), Dodecenoic acid (all ), Tridecenoic acid (including all isomers), tetradecenoic acid (including all isomers), pentadecenoic acid (including all isomers), hexadecenoic acid (including all isomers), Heptadecenoic acid (including all isomers), octadecenoic acid (including all isomers), nonadecenoic acid (including all isomers), icosenoic acid (including all isomers), heicosenoic acid (all isomers) ), Docosenoic acid (including all isomers), tricosenoic acid (including all isomers), tetracosenoic acid (including all isomers), pentacosenoic acid (including all isomers), hexacosene Acid (including all isomers), Heptacosenic acid (including all isomers), Octacosenic acid (including all isomers), Nonacenoic acid (including all isomers), Triacontenoic acid (all Unsaturated fatty acids), and mixtures thereof.

  Moreover, you may use hydroxycarboxylic acid as carboxylic acid which comprises partial ester. The “hydroxycarboxylic acid” in the present invention means a carboxylic acid having a hydroxyl group in addition to the hydroxyl group contained in the carboxylic acid group (—COOH).

  The hydroxycarboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, but is preferably a saturated carboxylic acid from the viewpoint of stability. Further, the hydroxycarboxylic acid may be a linear carboxylic acid or a branched carboxylic acid, but the linear carboxylic acid or 1 to 2 branched chains having 1 or 2 carbon atoms (more preferably 1 carbon atoms) ( More preferably, it is a branched carboxylic acid having 1 to 2, particularly preferably 1).

  Moreover, it is preferable that it is 2-40 from the point of coexistence with rust prevention property and storage stability, as for carbon number of hydroxycarboxylic acid, it is more preferable that it is 6-30, and it is 8-24. Further preferred.

  The number of carboxylic acid groups that the hydroxycarboxylic acid has is not particularly limited, and may be either the hydroxycarboxylic acid monobasic acid or the polybasic acid, but is preferably a monobasic acid.

  In addition, the number of hydroxyl groups that the hydroxycarboxylic acid has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, more preferably 1 to 2 from the viewpoint of stability. Is more preferable and one is particularly preferable.

  Further, the bonding position of the hydroxyl group in the hydroxycarboxylic acid is arbitrary, but the carboxylic acid in which the hydroxyl group is bonded to the bonding carbon atom of the carboxylic acid group (α-hydroxy acid), and the main chain as viewed from the bonding carbon atom of the carboxylic acid group. A carboxylic acid having a hydroxyl group bonded to the carbon atom at the other end (ω-hydroxy acid) is preferred.

  Preferable examples of the hydroxycarboxylic acid include α-hydroxy acid represented by the following general formula (1) and ω-hydroxy acid represented by the following general formula (2).

［式中、Ｒ^１は水素原子、炭素数１〜３８のアルキル基又は炭素数２〜３８のアルケニル基を示す。］

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 38 carbon atoms, or an alkenyl group having 2 to 38 carbon atoms. ]

［式中、Ｒ^２は水素原子、炭素数１〜３８のアルキレン基又は炭素数２〜３８のアルケニレン基を示す。］

[Wherein, R ² represents a hydrogen atom, an alkylene group having 1 to 38 carbon atoms, or an alkenylene group having 2 to 38 carbon atoms. ]

In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 38 carbon atoms, or an alkenyl group having 1 to 38 carbon atoms. Specific examples of the alkyl group and alkenyl group represented by R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl Group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group Alkyl etc. Group (including all isomers): ethenyl group (vinyl group), propenyl group (allyl group), butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group , Tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicosenyl group, dococenyl group, tricosenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, heptacocenyl group, heptacocenyl group, heptacocenyl group Group, triacontenyl group, hentriacontenyl group, dotriacontenyl group, tritriacontenyl group, tetratriacontenyl group, pentatriacontenyl group, hexatriacontenyl group, heptatri Konteniru group, (including all isomers) alkenyl groups such as octa thoria Conte sulfonyl group and the like.

In the general formula (2), R ² represents a hydrogen atom, an alkylene group having 1 to 38 carbon atoms, or an alkenylene group having 2 to 38 carbon atoms. Specific examples of the alkylene group and alkenylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and an undecylene group. , Dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, heicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacene group Group, octacosylene group, nonacosylene group, triacontylene group, hentriacontylene group, dotriacontylene group, tritriacontylene group, tetratriacontylene group, pentatriacontylene group, hexato Alkylene groups (including all isomers) such as rear contylene group, heptatria acetylene group, octatria contylene group; ethenylene group (vinylene group), propenyl group (arylene group), butenylene group, pentenylene group, hexenylene group, Heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group, dodecenylene group, tridecenylene group, tetradecenylene group, pentadecenylene group, hexadecenylene group, heptadecenylene group, octadecenylene group, nonadecenylene group, icocenylene group, icocenylene group, Tetracosenylene group, Pentacosenylene group, Hexacosenylene group, Heptacosenylene group, Octacocenylene group, Nonacosenylene group, Triacontenylene group, Hentriaconte Alkenylene groups such as Len, Dotria Contenylene, Tritria Contenylene, Tetratria Contenylene, Pentatria Contenylene, Hexatria Contenylene, Heptatria Contenylene, Octatria Contenylene, etc. (all Isomers) and the like.

  As a raw material containing such a hydroxycarboxylic acid, a lanolin fatty acid obtained by purifying (hydrolyzing etc.) a waxy substance adhering to sheep wool can be preferably used.

  When hydroxycarboxylic acid is used as the constituent carboxylic acid of the partial ester, a carboxylic acid having no hydroxyl group may be used in combination. The “carboxylic acid having no hydroxyl group” in the present invention means a carboxylic acid having no hydroxyl group other than the hydroxyl group contained in the carboxylic acid group (—COOH).

  In addition, when the carboxylic acid which comprises partial ester contains both the hydroxycarboxylic acid and the carboxylic acid which does not have a hydroxyl group, it is preferable that the ratio of the hydroxycarboxylic acid to the whole quantity of constituent carboxylic acid is 5-80 mass%. . When the proportion of hydroxycarboxylic acid is less than 5% by mass, the rust prevention property tends to be insufficient. For the same reason, the hydroxycarboxylic acid ratio is more preferably 10% by mass or more, and further preferably 15% by mass or more. Moreover, when the ratio of the said hydroxycarboxylic acid exceeds 80 mass%, it exists in the tendency for storage stability and the solubility with respect to base oil to become inadequate. For the same reason, the proportion of the hydroxycarboxylic acid is more preferably 60% by mass or less, further preferably 40% by mass or less, still more preferably 30% by mass or less, and 20% by mass or less. It is particularly preferred that

  The carboxylic acid having no hydroxyl group may be a saturated carboxylic acid or an unsaturated carboxylic acid.

  Of the carboxylic acids having no hydroxyl group, the saturated carboxylic acid may be either a straight-chain carboxylic acid or a branched carboxylic acid, but the straight-chain carboxylic acid or 1 or 2 carbon atoms (more preferably 1 carbon atom). A branched carboxylic acid having 1 to 3 (more preferably 1 to 2 and still more preferably 1) branched chains is preferable.

  The number of carbon atoms of the saturated carboxylic acid having no hydroxyl group is preferably 2 to 40, more preferably 6 to 30, and more preferably 8 to 24 from the viewpoint of achieving both rust prevention and storage stability. More preferably it is.

  The number of carboxylic acid groups in the saturated carboxylic acid having no hydroxyl group is not particularly limited and may be either a monobasic acid or a polybasic acid, but is preferably a monobasic acid.

  Among saturated carboxylic acids having no hydroxyl group, linear saturated carboxylic acids having 10 to 16 carbon atoms such as lauric acid and stearic acid are particularly preferable from the viewpoint of oxidation stability and stain resistance.

  Of the carboxylic acids having no hydroxyl group, the unsaturated carboxylic acid may be either a straight-chain carboxylic acid or a branched carboxylic acid, or a straight-chain carboxylic acid, or 1 or 2 carbon atoms (more preferably 1 carbon atoms). ) Is preferably a branched carboxylic acid having 1 to 3 (more preferably 1 to 2 and even more preferably 1) branched chains.

  Moreover, among the carboxylic acids having no hydroxyl group, the number of carbon atoms of the unsaturated carboxylic acid is preferably 2 to 40, and preferably 6 to 30 in terms of both rust prevention and storage stability. Is more preferable, it is still more preferable that it is 8-24, and it is especially preferable that it is 12-22.

  The number of carboxylic acid groups in the unsaturated carboxylic acid having no hydroxyl group is not particularly limited and may be either a monobasic acid or a polybasic acid, but is preferably a monobasic acid.

  The number of unsaturated bonds of the unsaturated carboxylic acid having no hydroxyl group is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of stability. More preferably, it is ˜2 and particularly preferably 1.

  Among unsaturated carboxylic acids having no hydroxyl group, linear unsaturated carboxylic acids having 18 to 22 carbon atoms such as oleic acid are preferable from the viewpoint of rust prevention and solubility in base oil, and oxidation stability, From the viewpoint of solubility in base oil and stain resistance, branched unsaturated carboxylic acids having 18 to 22 carbon atoms such as isostearic acid are preferable, and oleic acid is particularly preferable.

  In the partial ester of polyhydric alcohol and carboxylic acid, the proportion of unsaturated carboxylic acid in the constituent carboxylic acid is preferably 5 to 95% by mass. By making the ratio of unsaturated carboxylic acid 5 mass% or more, rust prevention property and storage stability can further be improved. For the same reason, the proportion of the unsaturated carboxylic acid is more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and 35% by mass. The above is particularly preferable. On the other hand, when the ratio of the unsaturated carboxylic acid exceeds 95% by mass, the air exposure property and the solubility in base oil tend to be insufficient. For the same reason, the proportion of the unsaturated carboxylic acid is more preferably 80% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

  The “unsaturated carboxylic acid” includes both unsaturated carboxylic acids having a hydroxyl group and unsaturated carboxylic acids having no hydroxyl group, but unsaturated carboxylic acids having no hydroxyl group in the total amount of unsaturated carboxylic acids. The ratio of the acid is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.

  When the partial ester is a partial ester in which the proportion of the unsaturated carboxylic acid in the constituent carboxylic acid is 5 to 95% by mass, the iodine value of the partial ester is preferably 5 to 75. More preferably, it is -60, and it is still more preferable that it is 20-45. When the iodine value of the partial ester is less than 5, rust prevention properties and storage stability tend to be lowered. Moreover, when the iodine value of a partial ester exceeds 75, it exists in the tendency for the air exposure property and the solubility with respect to a base oil to fall.

  The “iodine value” as used 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 unsaponified product value of chemical products”. .

Examples of the method for producing a partial ester preferably used in the present invention include the following production methods (i), (ii), and (iii).
(I) Partial ester of polyhydric alcohol and hydroxycarboxylic acid (or a mixture of hydroxycarboxylic acid and saturated carboxylic acid having no hydroxyl group) and unsaturated carboxylic acid (or hydroxyl group) having no polyhydric alcohol and hydroxyl group And a partial ester of a mixture of an unsaturated carboxylic acid having no carboxylic acid and a saturated carboxylic acid having no hydroxyl group) are mixed so that the carboxylic acid composition in the mixture of the two satisfies the above conditions.
(Ii) A carboxylic acid having a hydroxyl group and an unsaturated carboxylic acid having no hydroxyl group are mixed so that the carboxylic acid composition of the resulting partial ester satisfies the above conditions (or a saturated carboxylic acid having no hydroxyl group is mixed). Further mixing), a partial esterification reaction of the carboxylic acid mixture and polyhydric alcohol is performed.
(Iii) A partial ester of a mixture of a hydroxycarboxylic acid and an unsaturated carboxylic acid having no hydroxyl group (or a mixture of these carboxylic acid and a saturated carboxylic acid having no hydroxyl group) has a carboxylic acid composition as described above. A partial ester of a polyhydric alcohol and a hydroxycarboxylic acid (or a mixture of a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group) or an unsaturated carboxylic acid having no polyhydric alcohol and a hydroxyl group so as to satisfy the conditions A partial ester of (or a mixture of an unsaturated carboxylic acid having no hydroxyl group and a saturated carboxylic acid having no hydroxyl group) is mixed.

  For example, in the case of the production method (i), a lanolin fatty acid is used as a mixture of a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, and an unsaturated carboxylic acid having no hydroxyl group is an carboxylic acid having 2 to 40 carbon atoms. Unsaturated carboxylic acids can be preferably used. In this case, a partial ester (first partial ester) composed of a mixture of polyhydric alcohol, hydroxycarboxylic acid and saturated carboxylic acid having no hydroxyl group (preferably lanolin fatty acid), polyhydric alcohol and hydroxyl group The content ratio of the partial ester (second partial ester) composed of the unsaturated carboxylic acid (preferably oleic acid) that is not present is not particularly limited as long as the carboxylic acid composition ratio in the mixture satisfies the above conditions. However, the ratio of the first partial ester to the total amount of the first and second partial esters is preferably 20 to 95% by mass, more preferably 40 to 80% by mass, and 55 to 65%. It is particularly preferable that the content is% by mass. When the ratio of the first partial ester is less than 20% by mass or exceeds 95% by mass, rust prevention properties such as air exposure tend to be insufficient. Moreover, when the ratio of 1st partial ester exceeds 95 mass%, the solubility with respect to the base oil of the whole partial ester will fall, and it exists in the tendency for storage stability to become inadequate.

  The esterified oxidized wax refers to a product obtained by reacting an oxidized wax with an alcohol to esterify part or all of the acidic groups of the oxidized wax. Here, as the oxidized wax used as the raw material of the esterified oxidized wax, the oxidized wax exemplified in the description of the oxidized wax salt; the alcohols are linear or branched having 1 to 20 carbon atoms. Examples thereof include saturated monohydric alcohols, linear or branched unsaturated monohydric alcohols having 1 to 20 carbon atoms, polyhydric alcohols exemplified in the description of the ester, alcohols obtained by hydrolysis of lanolin, and the like. .

  The esterified lanolin fatty acid refers to a product obtained by reacting a lanolin fatty acid obtained by purifying (hydrolyzing, etc.) a waxy substance adhering to sheep wool and an alcohol. Here, examples of the alcohol used as a raw material for the esterified lanolin fatty acid include alcohols exemplified in the description of the esterified oxidized wax, and among them, polyhydric alcohols are preferable, and trimethylolpropane, trimethylolethane, and sorbitan. , Pentaerythritol and glycerin are more preferable.

  Examples of the alkyl or alkenyl succinic acid ester include esters of the above-described alkyl or alkenyl succinic acid with a monohydric alcohol or a dihydric or higher polyhydric alcohol. Among these, esters of monohydric alcohols and dihydric alcohols are preferable.

  The monohydric alcohol here may be a linear or branched one, and may be a saturated alcohol or an unsaturated alcohol. Moreover, although carbon number in particular of monohydric alcohol is not restrict | limited, C8-C18 aliphatic alcohol is used preferably.

  As the dihydric alcohol, alkylene glycol and polyoxyalkylene glycol are preferably used. Specific examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, and decylene glycol. Examples of the polyoxyalkylene glycol include those obtained by homopolymerization or copolymerization of a certain group side such as ethylene oxide, propylene oxide, butylene oxide. In the polyoxyalkylene glycol, when alkylene oxides having different structures are copolymerized, the polymerization form of the oxyalkylene group is not particularly limited, and may be random copolymerization or block copolymerization. Moreover, the polymerization degree of polyoxyalkylene glycol is not particularly limited, but is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.

  The alkyl or alkenyl succinic acid ester may be a diester in which both of two —COOH groups of the alkyl or alkenyl succinic acid are esterified (complete ester), or only one of the —COOH groups is an ester. Monoester (partial ester) may be used, but monoester is preferable from the viewpoint of more excellent rust prevention.

Moreover, as a sarcosine type compound, the compound represented by either of the following general formula (3)-(5) is used preferably. By including the sarcosine type compounds represented by the general formulas (3) to (5) in the rust preventive oil composition of the present invention, rust can be obtained without using heavy components such as wax, petrolatum, and heavy base oil. The ability to further improve the anti-corrosion property and maintain the anti-corrosion property at a high level for a long period of time. A rust preventive oil composition advantageous in terms of degreasing and sprayability can be obtained.
R ³ —CO—NR ⁴ — (CH ₂ ) _n —COOX (3)
(In the formula, R ³ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, X is a hydrogen atom, and an alkyl group having 1 to 30 carbon atoms. Or an alkenyl group having 1 to 30 carbon atoms, and n represents an integer of 1 to 4.)
_{^{[R 3 -CO-NR 4 -}} (CH 2) n -COO] m Y (4)
Wherein R ³ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, Y is an alkali metal or alkaline earth metal, and n is 1 An integer of ˜4, m is 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.
_{^{[R 3 -CO-NR 4 -}} (CH 2) n -COO] m -Z- (OH) m '(5)
(Wherein R ³ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, and Z is a hydroxyl group of a polyhydric alcohol having 2 or more valences) And m represents an integer of 1 or more, m ′ represents an integer of 0 or more, m + m ′ represents a valence of Z, and n represents an integer of 1 to 4.)
In general formulas (3) to (5), R ³ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms. From the viewpoint of solubility in base oil, the alkyl group or alkenyl group must have 6 or more carbon atoms, preferably 7 or more carbon atoms, and more preferably 8 or more carbon atoms. Further, from the viewpoint of storage stability and the like, it is necessary that the alkyl group or alkenyl group has 30 or less carbon atoms, preferably 24 or less carbon atoms, and more preferably 20 or less carbon atoms. Specific examples of such alkyl groups and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Alkyl groups such as heptadecyl group, octadecyl group, nonadecyl group, icosyl group (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like alkenyl groups (these alkenyl groups may be linear or branched, and the position of the double bond) Are also optional)

In general formulas (3) to (5), R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms. From the viewpoint of storage stability and the like, it is necessary that the alkyl group has 4 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms. In general formulas (3) to (5), n represents an integer of 1 to 4. From the viewpoint of storage stability and the like, it is necessary to be an integer of 4 or less, preferably 3 or less, and more preferably 2 or less.
In General Formula (3), X represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon atoms. The alkyl group or alkenyl group represented by X needs to have 30 or less carbon atoms from the viewpoint of storage stability, preferably 20 or less carbon atoms, and preferably 10 or less carbon atoms. More preferred. Specific examples of such an alkyl group or alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. (These alkyl groups may be linear or branched); alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group (these alkenyl groups) May be linear or branched, and the position of the double bond is arbitrary). Moreover, it is preferable that it is an alkyl group from the point of being excellent in rust prevention property. X is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms from the viewpoint of more excellent rust-preventing properties, and is preferably a hydrogen atom or 1 to 20 carbon atoms. It is more preferably an alkyl group, and even more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

  In the general formula (4), Y represents an alkali metal or an alkaline earth metal, and specific examples include sodium, potassium, magnesium, calcium, barium and the like. Among these, alkaline earth metals are preferable because they are more excellent in rust prevention. In addition, in the case of barium, there is a risk that the safety to the human body and the ecosystem will be insufficient. In the general formula (3), m represents 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.

  In general formula (5), Z represents the residue except the hydroxyl group of the polyhydric alcohol more than bivalence. Specific examples of such polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2- Octanediol, 1,8-octanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol Divalent alcohols such as glycerin, 2- (hydroxymethyl) -1,3-propanediol, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3 -Propanetriol, 2-methyl-2,3,4- Tantriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4 -Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, erythritol, 1, 2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan Tetrahydric alcohols such as adonitol, arabitol, xylitol, triglycerin, etc .; dipentaerythritol Le, sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as allose, polyglycerin or their dehydrated condensates and the like.

  In the general formula (5), m is an integer of 1 or more, m ′ is an integer of 0 or more, and m + m ′ is the same as the valence of Z. That is, all of the hydroxyl groups of the polyhydric alcohol of Z may be substituted, or only a part thereof may be substituted.

Among the sarcosine compounds represented by the above general formulas (3) to (5), it is at least one compound selected from the general formulas (3) and (4) from the viewpoint of more excellent rust prevention properties. It is preferable. Moreover, only 1 type of compound chosen from general formula (3)-(5) may be used independently, and the mixture of 2 or more types of compounds may be used.
Examples of the amine include amines exemplified in the description of the oxidized wax salt.

  In addition, examples of the boron compound include calcium borate.

  Further, in addition to the above rust inhibitor, alcohols represented by higher aliphatic alcohols; phosphoric acid monoesters, phosphoric acid diesters, phosphorous esters, (amine) phosphorus represented by amine salts thereof Acid derivatives and the like can also be included as rust inhibitors.

  In the rust preventive oil composition of the present invention, one of the rust preventive additives may be used alone, or two or more may be mixed and used. However, in the rust preventive oil composition of the present invention containing carboxylic acid as an essential component, it is preferable to use a sulfonate because higher rust preventive properties can be obtained. Furthermore, when using a sulfonate, you may further contain at least 1 sort (s) chosen from carboxylate, ester, a sarcosine type compound, an amine, and a boron compound. Furthermore, the rust inhibitor used in combination with the sulfonate is preferably at least one selected from esters and carboxylates, and more preferably used in combination with esters and carboxylates. In addition, as the ester herein, a partial ester of polyhydric alcohol and a partial ester of alkenyl succinic acid are preferable. As the carboxylic acid, fatty acid, dimer acid and alkenyl succinic acid are preferable. As the carboxylate, a fatty acid salt and Lanolin fatty acid salts are preferred.

  In the rust prevention composition of the present invention, the content of rust prevention additives other than oxidized wax and carboxylic acid is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1. ˜20 mass%. When the content of the rust prevention additive is less than the lower limit, the effect of improving the rust prevention property due to the addition tends to be insufficient. Moreover, even if content of the said rust prevention additive exceeds 40 mass%, it exists in the tendency for the improvement effect of the rust prevention property corresponding to content not to be acquired.

  Further, the rust preventive oil composition of the invention may further contain other additives as necessary. Here, specific examples of other additives used in the present invention include, for example, paraffin wax having a remarkable effect of improving the rust-preventing property in an acidic atmosphere; Fats and oils, sulfurized esters, phosphate esters such as long-chain alkyl zinc dithiophosphates, tricresyl phosphates, fats and oils such as pork fats, fatty acids, higher alcohols, calcium carbonate, potassium borate; phenols to improve antioxidant performance Or amine antioxidants; corrosion inhibitors for improving corrosion prevention performance (benzotriazole or its derivatives, thiadiazole, benzothiazole, etc.); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, microwax , Slack wack , Polyolefin waxes, film-forming agents such as petrolatum; methyl silicone, fluorosilicone, antifoaming agents such as polyacrylates, water-soluble spoilage factors water and surfactant to remove, and mixtures thereof.

  Further, the base number of the rust-preventing oil composition of the present invention is not particularly limited, but from the viewpoint of rust prevention properties, the base number is preferably 1 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, and still more preferably. Is 2 mgKOH / g or more, particularly preferably 3 mgKOH / g or more. From the viewpoint of storage stability, the base number is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, still more preferably 10 mgKOH / g or less, and particularly preferably 8 mgKOH / g. The base number referred to here is 6. JIS K 2501 “Petroleum products and lubricants—neutralization number test method”. The base number [mgKOH / g] measured by the hydrochloric acid method according to the above.

Further, the kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is not particularly limited, but is preferably 1 mm ² / s or more, more preferably 2 mm ² / s or more, further preferably 2.5 mm ² / s or more, More preferably, it is 3 mm < ² > / s or more, Most preferably, it is 3.5 mm < ² > / s or more. When the kinematic viscosity at 40 ° C. of the rust-preventing oil composition is less than the lower limit value, the oil film of the coating film is likely to break, and the rust-preventing property tends to be insufficient. Moreover, the kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is preferably 50 mm ² / s or less, more preferably 40 mm ² / s or less, and further preferably 30 mm ² / s or less. When the kinematic viscosity at 40 ° C. of the rust preventive oil composition exceeds the upper limit, workability tends to be lowered.

Even when the viscosity of the rust preventive composition of the present invention is high, by applying the kinematic viscosity to a predetermined value or less (preferably 50 mm ² / s or less) by heating to the object to be treated, The composition can be easily and reliably applied to an object to be processed. However, when the kinematic viscosity at 40 ° C. of the rust-preventing oil composition exceeds 1000 mm ² / s, heating at a higher temperature is required to reduce the viscosity, which promotes deterioration of the rust-preventing oil. Performance will be impaired. Therefore, the kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is preferably 1000 mm ² / s or less.

  The rust preventive oil composition of the present invention having the above configuration can achieve all of rust preventive properties, degreasing properties and storage stability at a high level in a balanced manner, and is suitable as a rust preventive oil for various metal members. Can be used. There are no particular restrictions on the metal member that is the object to be treated. Specifically, it is a cold-rolled steel sheet, hot-rolled steel sheet, high-tensile latter half, galvanized steel sheet, etc. Examples thereof include metal plate materials such as an original plate, an aluminum alloy plate, and a magnesium alloy plate, and further bearing components such as a rolling bearing, a tapered rolling bearing, and a needle bearing, an architectural steel material, and a precision component.

  As rust prevention oil for such metal members, intermediate rust prevention oil used in the process of processing metal members, shipping rust prevention oil used for rust prevention at the time of shipment, before being subjected to press working There are cleaning rust preventive oils used in the cleaning process for removing foreign substances in the metal plate manufacturer or prior to shipping in the metal plate manufacturer, but the rust preventive oil composition of the present invention should be used for any of the above applications. Can do.

  Moreover, the method in particular of apply | coating the rust prevention oil composition of this invention to a to-be-processed object is not restrict | limited, For example, it applies to metal members by methods, such as spray, dripping, the transfer by a felt material, electrostatic oiling. be able to. Among these coating methods, the spray method is preferable because the oil film thickness can be made uniform by coating in a fine mist. The application apparatus in the case of applying the spray method is not particularly limited as long as it can atomize the rust preventive oil composition, and for example, any of an air spray type, an airless spray type, a hot melt type and the like can be applied. .

  Furthermore, in the coating process, it is preferable to provide a drain cutting process using a centrifuge or a drain cutting process by leaving for a long time after an excessive rust preventive oil composition is coated.

  Further, when the rust-preventing oil composition of the present invention is used as a cleaning rust-preventing oil composition, a large excess amount of the rust-preventing oil composition of the present invention is sprayed, showered, or dipped on the surface of a metal member. Good cleaning and subsequent rust prevention can be performed by refueling. Furthermore, if the surface cleaning with a roll brush or the like is performed after the above-described metal processing step as necessary, the efficiency of removing foreign matters can be enhanced. Furthermore, when performing cleaning using the rust preventive oil composition of the present invention, it is possible to adjust the amount of oil adhering to the surface of the metal member by performing surface treatment of the metal member with a ringer roll or the like. preferable.

  Regardless of the application method of the rust-preventing oil composition of the present invention, it is preferable to recover, circulate and reuse the rust-preventing oil composition applied in excess on the metal member. It should be noted that when the rust preventive oil composition is circulated, it is preferable to remove foreign matters mixed in the circulation system. Specifically, for example, a foreign substance can be removed by providing a filter in the course of the circulation path of the rust preventive oil composition of the present invention, preferably immediately before the rust preventive oil composition is jetted toward the metal member. it can. Moreover, a magnet can be provided in the bottom part of the tank which stores the rust prevention oil composition of this invention, and foreign matters, such as an abrasion part, can also be adsorb | sucked and removed by magnetic force. In addition, there is a concern that the performance of the rust preventive oil composition of the present invention that is reused in such a process is deteriorated due to contamination of the oil in the previous process. Therefore, when reusing the rust-preventing oil composition of the present invention, the properties are controlled by periodically measuring the kinematic viscosity and density, copper plate corrosion test, rust-preventing property test, etc. on the oil used. It is preferable to perform oil renewal, drain disposal, tank cleaning, oil purification operation, etc. as necessary. Furthermore, the discarded oil is used as it is or diluted with a solvent or a low-viscosity base oil, and used in a line where the required performance for the rust prevention oil composition is lower than the line used before disposal. As a result, the total amount of oil used can be reduced. Furthermore, when the rust preventive oil composition of the present invention is stored in a tank, it is preferably replenished according to the amount of decrease in the composition in the tank. In that case, it may not necessarily be the same composition as the rust-preventing oil composition filled in the initial stage, but a composition with an increased amount of additives for drawing out the performance to be enhanced may be replenished depending on the occasion. Alternatively, conversely, the cleaning ability of the rust-preventing oil composition may be maintained by replenishing a composition having a reduced viscosity by a method such as reducing the content of the high-viscosity base oil.

  In addition, when the rust preventive oil composition of the present invention is used in a cleaning process for removing foreign matters prior to shipment at a metal plate manufacturer, the metal plate is wound up in a coil shape immediately after the cleaning process or stacked as a sheet material. Can be shipped. That is, the rust preventive oil composition of the present invention can be used as a cleaning rust preventive oil and a shipping rust preventive oil. According to this method, there is a merit that the amount of foreign matter attached is small and cleaning can be performed easily and reliably even when a cleaning process using a cleaning rust preventive oil is performed immediately before the pressing process in pressing. As a matter of course, a rust-preventing treatment may be performed in two stages by providing a step of applying rust-preventing oil again after the step of washing with the cleaning rust-preventing oil at the steel plate manufacturing site.

  The above-described hydrocarbon oil of the present invention is used as a base oil for rust prevention oil, but can also be used for other applications. Other applications include two-cycle engine oils, cleaning agents, various ink and paint solvents, cleaning solvents, aerosol solvents, preservatives, insecticides, pesticide solvents, pressure sensitive paper solvents, surface activity Diluents for agents, diluents for waxes, cleaners and polishes, automotive undercoat agents, dyeing solvents, organosols, pigment dispersants, blanket cleaners, semiconductor cleaners, pretreatment agents for plating, various lubricants, tire manufacture , Adhesives, mold release agents, polyolefin reaction solvents, household cleaners, NAD paints, ore flotation, printing ink cleaning solutions, car temporary protective paint (based on wax) removers, wood preservatives, herbicides Non-carbon paper, water treatment agents, diluents for metal extraction, CO2 production for greenhouses, metal deep wound agents, etc. The hydrocarbon oil of the present invention has characteristics such that it has little odor, can improve the working environment, and has little adverse effect on rubber or plastic parts around the place where it is used.

[Examples and Comparative Examples]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
In Examples and Comparative Examples, rust preventive oil compositions were prepared using the base oils in Table 1 at the blending ratios shown in Table 2. The components used for the preparation of each rust preventive oil composition are as follows.
(1) Manufacturing method of base oil to be used (FT synthetic oil hydrorefined oil, wax hydrocracked oil, and base oil 1, 2, 6, 7)
1) FT synthetic hydrocarbon oil made from natural gas as raw material (content of hydrocarbons with a boiling point of 150 ° C or higher: 82% by mass, content of hydrocarbons with a boiling point of 360 ° C or higher: 41% by mass) in a distillation column It was separated into a light fraction having a temperature of 150 ° C. or lower, an intermediate fraction having a boiling point of 150 to 360 ° C., and a heavy wax residue (FT wax: corresponding to a fraction having a boiling point of 360 ° C. or higher).
2) The middle distillate separated in 1) was a hydrorefining catalyst (Pt: 0.8% by mass with respect to the support, USY zeolite / silica alumina / alumina binder: weight ratio 3/57/40), under a hydrogen stream. The hydrorefining treatment was performed at a reaction temperature of 311 ° C., a hydrogen pressure of 3.0 MPa, LHSV: 2.0 h-1, and a hydrogen / oil ratio of 340 NL / L.
3) The hydrorefined oil obtained in 2) was fractionated by distillation into a 150 to 250 ° C. fraction (kerosene fraction 1) and a 250 to 360 ° C. fraction (light oil fraction 1).
4) The FT wax obtained in 1) was obtained by using a hydrogenolysis catalyst (Pt: 0.8% by mass with respect to the support, USY zeolite / silica alumina / alumina binder: weight ratio 3/57/40). Then, hydrogenolysis was performed at a reaction temperature of 326 ° C., a hydrogen pressure of 4.0 MPa, LHSV: 2.0 h−1, and a hydrogen / oil ratio of 680 NL / L.
5) The hydrocracked oil obtained in 4) was fractionated by distillation into a 150 to 250 ° C. fraction (kerosene fraction 2) and a 250 to 360 ° C. fraction (light oil fraction 2).
6) Gas oil fractions 1 and 2 obtained in 3) and 5) were mixed at 51:49 (mass ratio) to obtain dilute base oil 1. Properties of the base oil 1 are shown in Table 1.
7) Kerosene fractions 1 and 2 obtained in 3) and 5) were mixed at 63:37 (mass ratio) to obtain base oil 2. Properties of the base oil 2 are shown in Table 1.
8) The light oil fractions 1 and 2 obtained in 3) and 5) were mixed at 57:43 (mass ratio) to obtain a diluted base oil 6. Table 1 shows the properties of the base oil 6.
9) Kerosene fractions 1 and 2 obtained in 3) and 5) were mixed at 49:51 (mass ratio) to obtain base oil 7. The properties of the base oil 7 are shown in Table 1.
(Base oil 3-5)
1) The base oil 3 was a general hydrorefined mineral oil. Table 1 shows the properties of the base oil 3.
2) As the base oil 4, a general hydrorefined mineral oil was used. Table 1 shows the properties of the base oil 4.
3) As the base oil 5, a general hydrorefined mineral oil was used. Table 1 shows the properties of the base oil 5.

  In Examples and Comparative Examples, rust prevention oil compositions having the compositions shown in Table 2 were prepared using the base oils shown in Table 1 and the additives shown below.

The additives listed in Table 2 blended with the rust preventive oil are as follows.
(Additive)
A1: Alkylbenzene calcium sulfonate A2: Calcium salt of oxidized wax A3: Ester of polyhydric alcohol B1: Di-tert-butyl-p-cresol

Resin compatibility test The compatibility with the resin was tested by the following method.
Test method: The resin to be evaluated (50 mm × 50 mm × 5 mm) is completely immersed in 300 ml of sample oil. Then, hold | maintain for 30 days at 25 +/- 3 degreeC, and measure a volume change rate.
Evaluation method: A volume change rate of less than 10% is evaluated as ○, and 10% or more is evaluated as ×.
Type of resin to be evaluated: polyethylene resin, NBR rubber test:
In addition, wetting test JIS K2246 compliant and salt spray test JIS K2246 compliant were performed.
The results are shown in Table 2.

Claims (3)

The density at 15 ° C. is 0.7 to 0.8 g / cm ³ , the n-paraffin content is 20 to 80 % by mass , the aromatic content is 0 to 3% by volume , the naphthene content is 0 to 20% by volume , and the initial distillation. A hydrocarbon oil having a point of 140 to 280 ° C. and a 10% distillation point of 150 to 270 ° C. is 85% by mass or more based on the total amount of the composition, and the hydrocarbon oil is a Fischer-Tropsch (FT) synthesis step, Rust prevention characterized by being a kerosene fraction produced by a production process having at least one process selected from hydrocracking processes of wax-containing components and hydrorefining treatment processes of components obtained from these processes Oil composition. The density at 15 ° C. is 0.7 to 0.8 g / cm ³ , the n-paraffin content is 20 to 80 % by mass , the aromatic content is 0 to 3% by volume , the naphthene content is 0 to 20% by volume , and the initial distillation. Containing hydrocarbon oil with a point of 140-280 ° C, 10% distillation point of 150-270 ° C,
The hydrocarbon oil is produced by a production process having at least one process selected from a Fischer-Tropsch (FT) synthesis process, a hydrocracking process of wax-containing components, and a hydrorefining process of components obtained from these processes. A kerosene oil fraction,
If the kinematic viscosity of the hydrocarbon oil in 40 ° C. other than the hydrocarbon oil is present use by mixing a base oil of more than 6 mm 2 / ^s, the content of said hydrocarbon oil, rust preventive oil composition the total amount The solvent dilution type rust prevention oil composition which is 5-95 mass%.   The rust preventive oil composition according to claim 1 or 2, further comprising at least one selected from an oxidized wax salt, carboxylic acid, sulfonate, carboxylate, ester, sarcosine type compound, amine and boron compound.