JP6810933B2 - Anti-corrosion oil composition for iron products coated with iron oxide - Google Patents

Description

The present invention relates to a rust preventive oil composition for iron products and an iron product with an organic coating.

It is a generally known matter that iron oxidizes and rusts. Therefore, a rust preventive oil composition containing a rust preventive agent for preventing the occurrence of rust is applied to the surface of an iron product made of steel.

As the rust preventive agent contained in the rust preventive oil composition, many kinds such as fatty acid amine salt, metal sulfonate, amines, carboxylate, ester compound, sarcosine derivative, paraffin wax, oxide wax salt, boron compound and the like. It has been known. Further, usually, the rust preventive oil composition contains a base oil containing mineral oil or synthetic oil as a main component in addition to the rust preventive agent.

For example, Patent Document 1 describes a rust preventive oil composition using mineral oil as a base oil and lanolin fatty acid ester of dinonylnaphthalene sulfonate Na salt, ethylenediamine sulfonate and pentaerythritol as a rust preventive in 2% by mass, respectively. Has been done.

In Patent Document 2, a plurality of types of base oils composed of mineral oils or synthetic oils are used, and as a rust preventive, calcium sulfonate is 4.7% by mass, sorbitan monooleate is 1% by mass, and lanolin fatty acid ester of pentaerythritol is 2% by mass. The rust preventive oil composition used in% is described.

In Patent Document 3, mineral oil is used as a base oil, and trimethylolpropane ester is used as a rust preventive in an amount of 4% by mass, perbasic calcium sulfonate is used in an amount of 3% by mass, and neutral calcium sulfonate is used in an amount of 3% by mass. The composition is described.

Patent Document 4 describes a rust preventive oil composition using mineral oil as a base oil, barium dinonylnaphthalene sulfonate as a rust preventive in 13% by mass, and sorbitan monoisostearate in 7% by mass.

Patent No. 4728157 Patent No. 5550492 Japanese Unexamined Patent Publication No. 2007-153962 Japanese Unexamined Patent Publication No. 07-118685

By the way, it is known that the characteristics of an iron product can be suitably controlled by heat-treating an iron product made of steel at a high temperature. For example, in order to convert carbon steel, which is a kind of steel, to austenitization, for example, austenitization is known in which the austenitizing temperature is heated to 820 to 900 ° C. ing. In addition to the austempering treatment, a marquenching treatment, a maltempering treatment, an ausforming treatment, etc., in which the mode of cooling after heating is changed, are also known. Here, when the iron product in a high temperature state after the heat treatment comes into contact with the atmosphere, the surface thereof is oxidized and a film of iron oxide called black skin is formed on the surface of the iron product. Therefore, conventionally, the black skin formed on the surface of the iron product after the heat treatment is removed by a chemical treatment or a physical treatment, and then the rust preventive oil composition is directly applied to the surface of the iron product.

However, since the number of steps is increased due to the step of removing the black skin, the conventional method of applying the rust preventive oil composition is not always efficient. In addition, it was difficult to introduce equipment that shuts off the atmosphere in all processes from heat treatment to cooling from the viewpoint of equipment design and capital investment.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a new technique for applying a rust preventive oil composition to an iron product coated with iron oxide.

The present inventor aimed to utilize the black skin itself as an antioxidant film for iron products, instead of removing the black skin. As a result of diligent studies by the present inventor, a rust preventive oil composition containing three specific types of rust preventives and two specific types of base oil is superior to iron products coated with black skin. It was discovered that it has a rust preventive effect. Based on such findings, the present inventor has completed the present invention.

The rust preventive oil composition for iron products coated with iron oxide of the present invention
A corrosion inhibitor containing a metal sulfonate and a fatty acid metal salt and an ester compound, a kinematic viscosity at 40 ° C. and the first base oil is 2 to 50 mm ² / s, kinematic viscosity at 40 ℃ 300~600mm ² / A rust preventive oil composition containing a second base oil, which is s, and an organic solvent.
The ratio of the rust preventive agent to the entire rust preventive oil composition is 15 to 30% by mass, the ratio of the first base oil is 2 to 10% by mass, and the ratio of the second base oil is 28 to 50% by mass. It is characterized by being.

Further, the iron product with an organic coating of the present invention is characterized by having an organic coating formed by removing an organic solvent from the rust preventive oil composition of the present invention on the surface of the iron product coated with iron oxide. Hereinafter, in the description of the iron product with an organic coating of the present invention, the portion of the iron product with an organic coating of the present invention that is not coated with iron oxide and the organic coating may be referred to as an iron product body, and iron oxide. Iron products covered only with iron are sometimes called iron product intermediates.

According to the present invention, it is possible to provide a new technique for applying a rust preventive oil composition to an iron product coated with iron oxide.

It is a chromatogram which analyzed the mixed oil which mixed the 1st base oil and the 2nd base oil.

The best mode for carrying out the present invention will be described below. Unless otherwise specified, the numerical range "x to y" described in the present specification includes the lower limit x and the upper limit y. Then, a numerical range can be constructed by arbitrarily combining these upper and lower limit values and the numerical values listed in the examples. Further, a numerical value arbitrarily selected from these numerical values can be used as a new upper limit or lower limit numerical value.

The rust preventive oil composition for iron products coated with iron oxide of the present invention (hereinafter, may be simply referred to as "the rust preventive oil composition of the present invention").
A corrosion inhibitor containing a metal sulfonate and a fatty acid metal salt and an ester compound, a kinematic viscosity at 40 ° C. and the first base oil is 2 to 50 mm ² / s, kinematic viscosity at 40 ℃ 300~600mm ² / A rust preventive oil composition containing a second base oil, which is s, and an organic solvent.
The ratio of the rust preventive agent to the entire rust preventive oil composition is 15 to 30% by mass, the ratio of the first base oil is 2 to 10% by mass, and the ratio of the second base oil is 28 to 50% by mass. It is characterized by being.

The rust preventive oil composition of the present invention contains three types of rust preventive agents, which are a metal sulfonate, a fatty acid metal salt, and an ester compound. All three types of rust preventives have a polar group and a lipophilic group. In the organic coating of the iron product with an organic coating of the present invention, it is considered that the polar groups of the three types of rust preventives play a role of adsorbing and / or binding to the iron product body and / or iron oxide. It is known that the surface of black skin, which is iron oxide, is uneven. In the iron product with an organic coating of the present invention, the rust preventive penetrates deep into the depression on the surface of the black skin, and the polar group of the rust preventive strongly adsorbs and / or binds to the deep part of the black skin. There is expected. Further, the lipophilic group of the three types of rust preventives is considered to play a role of improving the affinity for the base oil.

The "iron oxide" in the rust preventive oil composition of the present invention and the iron product with an organic coating of the present invention is called black skin or black rust, and Fe ₃ O ₄ which is triiron tetroxide is used. means.

As the metal sulfonate, a known metal sulfonate used as a rust preventive may be adopted. From the viewpoint of chemical structure, metal sulfonate means a salt of an alkali metal or alkaline earth metal and an organic sulfonic acid. As the metal sulfonate, a single compound may be adopted, or a mixture in which a plurality of compounds are mixed may be adopted. Examples of the alkali metal of the metal sulfonate include lithium, sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium and barium.

Examples of the organic sulfonic acid in the metal sulfonate include mineral oil sulfonic acid made from mineral oil and alkyl aromatic sulfonic acid. Mineral oil sulfonic acid is an organic sulfonic acid including an alkyl aromatic sulfonic acid. Alkyl aromatic sulfonic acids can be produced, for example, by sulfonic oxidation of alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700. As the mineral oil sulfonic acid, a sulfonic acid obtained by sulfonated an alkyl aromatic compound of a lubricating oil fraction of the mineral oil or a petroleum sulfonic acid produced as a by-product during paraffin production may be adopted.

Examples of the aromatic in the alkyl aromatic sulfonic acid include benzene and naphthalene.

The alkyl in the alkyl aromatic sulfonic acid may be a linear alkyl or a branched chain alkyl. Examples of the number of carbon atoms of the alkyl group include 1 to 30, preferably 2 to 24, and more preferably 6 to 18. The number of alkyls bonded to the aromatic is preferably 1 to 3, more preferably 1 to 2, and even more preferably 2. Specific examples of alkyls include octyl, nonyl, decyl, dodecyl, and octadecyl.

Specific examples of the metal sulfonate include mineral oil barium sulfonic acid salt, barium dialkylnaphthalenesulfonate, calcium dialkylnaphthalenesulfonate, calcium dialkylbenzenesulfonate, barium dodecylbenzenesulfonate, and sodium dodecylbenzenesulfonate.

As the fatty acid metal salt, a known fatty acid metal salt used as a rust preventive may be adopted. From the viewpoint of chemical structure, a fatty acid metal salt means a salt of an alkali metal or an alkaline earth metal and a fatty acid. As the fatty acid metal salt, a single compound may be adopted, or a mixture in which a plurality of compounds are mixed may be adopted. Examples of the alkali metal of the fatty acid metal salt include lithium, sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium and barium.

Fatty acids in fatty acid metal salts include single compounds such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, behenic acid, and serotic acid, and avietin. Examples thereof include mixtures of acids, linolenic acids, lanolin fatty acids and the like. The carbon number of the carbon chain of the fatty acid is preferably 8 to 30, more preferably 10 to 24. The carbon chain of the fatty acid is a saturated or unsaturated chain, and the carbon chain may have a substituent such as a hydroxyl group.

Examples of suitable fatty acid metal salts include lanolin fatty acid calcium salt, lanolin fatty acid magnesium salt, and lanolin fatty acid barium salt.

As the ester compound, a known ester compound used as a rust preventive may be adopted, and from the viewpoint of chemical structure, it means a reaction product of a carboxylic acid and an alcohol. As the ester compound, a single compound may be adopted, or a mixture in which a plurality of compounds are mixed may be adopted.

As the carboxylic acid moiety in the ester compound, the chemical structure described as a fatty acid in a fatty acid metal salt is suitable. Further, the alcohol moiety in the ester compound may be a monoalcohol or a polyhydric alcohol having a plurality of hydroxyl groups. When the alcohol moiety in the ester compound is a polyhydric alcohol, an ester compound in which all the hydroxyl groups of the alcohol have reacted with the carboxylic acid may be adopted, but a partial ester compound in which some of the plurality of hydroxyl groups of the alcohol has reacted with the carboxylic acid. It is preferable to adopt.

The number of hydroxyl groups in the polyhydric alcohol is preferably 2 to 10, more preferably 3 to 6. The carbon number of the polyhydric alcohol is preferably 2 to 20, more preferably 3 to 10. Specific examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitan.

Specific examples of the ester compound include a fatty acid ester compound of a polyhydric alcohol, an ester compound of an oxide wax, and a lanolin fatty acid ester. The lanolin fatty acid ester includes an ester of lanolin alcohol and fatty acid, and an ester of lanolin acid and monoalcohol or polyhydric alcohol.

In the rust preventive oil composition of the present invention, the rust preventive effect is remarkably exhibited by the coexistence of three kinds of rust preventive agents. Further, in the rust preventive oil composition of the present invention, the total ratio of the three types of rust preventive agents to the entire rust preventive oil composition is 15 to 30% by mass. A rust preventive oil composition in which the ratio of the rust preventive agent is too low may reduce the rust preventive effect, while a rust preventive oil composition in which the ratio of the rust preventive agent is too high may have a rust preventive agent due to the solubility. There is a risk of precipitation.

When the ratio of the metal sulfonate to the entire rust preventive oil composition is X% by mass, the ratio of the fatty acid metal salt is Y% by mass, and the ratio of the ester compound is Z% by mass, X, Y and Z are all the following conditions. It is preferable to satisfy.
3 ≦ X <15, 3 ≦ Y <15, 3 ≦ Z <15, 15 ≦ X + Y + Z ≦ 30

The following conditions can be independently exemplified as preferable ranges of X, Y, and Z.
4 ≦ X ≦ 13, 4 ≦ X ≦ 9, 6 ≦ X ≦ 13, 6 ≦ X ≦ 9;
4 ≦ Y ≦ 13, 4 ≦ Y ≦ 9, 6 ≦ Y ≦ 13, 6 ≦ Y ≦ 9;
4 ≦ Z ≦ 13, 4 ≦ Z ≦ 9, 6 ≦ Z ≦ 13, 6 ≦ Z ≦ 9;
18≤X + Y + Z≤27, 20≤X + Y + Z≤25, 21≤X + Y + Z≤24

In rust preventing oil composition of the present invention, 40 a first base oil kinematic viscosity of 2 to 50 mm ² / s at ° C., 40 kinematic viscosity at ° C. and the second group is 300~600mm ² / s Use oil together as base oil. The "kinematic viscosity at 40 ° C." in the present specification means a value measured by the kinematic viscosity test method described in JIS K 2283. The base oil serves as a barrier function in the organic coating of the iron product with an organic coating of the present invention to prevent the iron product body and / or iron oxide from coming into contact with oxygen and moisture in the atmosphere.

Since the first base oil has a relatively low viscosity, it has an excellent affinity with a rust preventive. Therefore, the first base oil serves as a solvent for dissolving the rust preventive in the rust preventive oil composition of the present invention. Further, the first base oil can be used as a rust preventive in the organic film of the iron product with an organic film of the present invention while retaining the oil-based portion of the iron product body and / or the rust preventive adsorbed on iron oxide. It is considered to play a role as an intermediate layer connecting the interface with the second base oil.

Kinematic viscosity of the first base oil is in the range of 2 to 50 mm ² / s, preferably in the range of 2 to 30 mm ² / s, more preferably in the range of 2~20mm ² / s, 3~20mm ² / The range of s is more preferable, and the range of 4 to 10 mm ² / s is particularly preferable. If a base oil having an excessively high kinematic viscosity is used as the first base oil, such a base oil has a poor affinity with the rust preventive, so that it has a function of dissolving the rust preventive and the iron product body and / or iron oxide. It is considered that the function of retaining the lipophilic portion of the adsorbed rust preventive cannot be satisfactorily exhibited. On the other hand, if a base oil having an excessively low kinematic viscosity is used as the first base oil, it is difficult to stay in the organic coating of the iron product with an organic coating of the present invention because such a base oil is highly volatile at room temperature. Become.

The ratio of the first base oil to the entire rust preventive oil composition is in the range of 2 to 10% by mass, preferably in the range of 3 to 7% by mass, and more preferably in the range of 4 to 6% by mass. .. If the proportion of the first base oil is too low, the effect of the expected role of the first base oil is reduced. On the other hand, if the ratio of the first base oil is too high, the ratio of the rust inhibitor and the second base oil is relatively low, which causes a problem.

It is considered that the second base oil mainly fulfills a barrier function in the organic coating of the iron product with an organic coating of the present invention. Since the second base oil having a relatively high viscosity is located on the outermost side of the organic coating of the iron product with an organic coating of the present invention, the infiltration of oxygen and water can be effectively suppressed.

Kinematic viscosity of the second base oil is in the range of 300~600mm ² / s, preferably in the range of 400 to 600 mm ² / s, in the range of 450~550mm ² / s is more preferable. If a base oil having an excessively high kinematic viscosity is used as the second base oil, the viscosity of the rust preventive oil composition of the present invention becomes high, which may hinder the application to iron products. On the other hand, if a base oil having an excessively low kinematic viscosity is used as the second base oil, it is considered that the barrier function is reduced because such a base oil has a relatively high fluidity.

The ratio of the second base oil to the entire rust preventive oil composition is in the range of 28 to 50% by mass, preferably in the range of 30 to 45% by mass, and more preferably in the range of 35 to 45% by mass. .. If the proportion of the secondary base oil is too low, the effect of the expected role of the secondary base oil is reduced. On the other hand, if the ratio of the second base oil is too high, the ratio of the rust inhibitor and the first base oil is relatively low, which causes a problem.

The total of the ratio of the first base oil and the ratio of the second base oil to the entire rust preventive oil composition is in the range of 30 to 60% by mass, preferably in the range of 35 to 55% by mass, and 40. More preferably, it is in the range of ~ 50% by mass. Further, it is preferable that the difference in kinematic viscosity between the first base oil and the second base oil at 40 ° C. is large. Examples of the range of the difference include 350 to 550 mm ² / s, 400 to 550 mm ² / s, 450 to 550 mm ² / s, and 480 to 500 mm ² / s.

As described above, the rust preventive oil composition of the present invention contains two types of base oils having significantly different kinematic viscosity ranges. Here, it can be said that there is a correlation between the kinematic viscosity of the base oil and the molecular weight of the base oil. Therefore, in the analysis chart in which the molecular weight distributions of the first base oil and the second base oil of the rust preventive oil composition of the present invention are measured, a peak derived from the first base oil is observed in a relatively low molecular weight region. And a peak derived from the second base oil is observed in the relatively high molecular weight region. Further, if the difference between the kinematic viscosity of the first base oil and the kinematic viscosity of the second base oil is large, it is derived from the first base oil in the analysis chart in the molecular weight distribution measurement for the first base oil and the second base oil. The difference between the peak detection position and the peak detection position derived from the second base oil is also largely observed. The same applies to the organic coating in the iron product with an organic coating of the present invention.

As a method for measuring the molecular weight distribution of the first base oil and the second base oil, chromatography such as gel permeation chromatography (GPC), high-speed atomic impact-mass spectrometry (FAB-MS), or matrix-assisted laser desorption / ionization -Mass spectrometry (MALDI-MS), electrospray ionization-mass spectrometry (ESI-MS), or atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) can be exemplified, but are versatile. From this point of view, GPC using an electrospray ionization meter or a differential refractive meter as a detector is preferable.

As a matter of course, whether or not a certain rust preventive oil composition or a certain organic coating contains the first base oil and the second base oil can be determined by analysis such as various chromatographys and various mass spectrometry methods. .. Specifically, whether or not a certain rust preventive oil composition contains the first base oil and the second base oil specified in the rust preventive oil composition of the present invention is determined by, for example, the rust preventive oil composition of the present invention. It can be determined by measuring the molecular weight distribution of a certain rust preventive oil composition under the same conditions and comparing the obtained analysis charts.

The first base oil and the second base oil are mainly composed of mineral oil or synthetic oil and can be used as the base oil of the rust preventive oil composition, which are distinguished by the kinematic viscosity at 40 ° C. do it. In terms of distinguishing the first base oil and the second base oil from the organic solvent described later, the first base oil and the second base oil have a vapor pressure of less than 1 atm at room temperature, and are usually at room temperature. Anything that is recognized as not evaporating may be adopted.

Examples of the mineral oil include paraffinic mineral oil, naphthenic mineral oil, light neutral oil, medium neutral oil, heavy neutral oil, and bright stock. Further, as the mineral oil, those subjected to purification such as hydrogenation purification, solvent removal, solvent extraction, solvent removal, contact removal, hydrocracking, sulfuric acid cleaning, and white clay treatment are preferable.

The synthetic oil includes polymers such as polyolefins, olefin copolymers, polybutenes, polyol esters, dibasic acid ester polymers, polyoxyalkylene glycols, and polyoxyalkylene glycol ethers, or common weights obtained by combining monomers that are constituents of these polymers. The coalescence can be exemplified.

The first base oil and the second base oil can also be specified at the aniline point specified in JIS K 2256. The aniline point means the lowest temperature at which an equal volume mixture of aniline and a sample exists as a uniform solution. As used herein, the term "aniline point" means a value measured by the test method described in JIS K 2256.

The aniline point of the first base oil is preferably in the range of 70 to 100 ° C, more preferably in the range of 70 to 90 ° C, and even more preferably in the range of 75 to 85 ° C. The aniline point of the second base oil is preferably in the range of 120 to 150 ° C., more preferably in the range of 125 to 145 ° C., and even more preferably in the range of 130 to 140 ° C. The aniline point of the entire base oil, which is a mixture of the first base oil and the second base oil, is preferably in the range of 110 to 130 ° C., more preferably in the range of 110 to 120 ° C., and in the range of 115 to 120 ° C. Is even more preferable. Generally, the lower the viscosity of the base oil, the lower the aniline point.

As described above, the rust preventive oil composition of the present invention contains three specific types of rust preventives and two specific types of base oils in a suitable ratio. The rust preventive oil composition of the present invention exerts an excellent rust preventive effect not only on iron products not coated with iron oxide but also on iron products coated with iron oxide. One aspect of a suitable rust preventive oil composition of the present invention is particularly excellent in rust preventive effect on iron products coated with iron oxide. That is, one aspect of the suitable rust preventive oil composition of the present invention is (the rust preventive oil composition) with respect to (the rust generation time of the iron product not coated with iron oxide treated with the rust preventive oil composition). The ratio of the rust generation time of the iron product coated with iron oxide treated in 1) is 1 or more. The term "rust" here means Fe ₂ O ₃ and / or Fe OOH, which is red rust, instead of Fe ₃ O ₄ , which is black skin that has been formed in advance.

The rust preventive oil composition of the present invention contains an organic solvent. The organic solvent is added for the purpose of improving the coatability of the rust preventive oil composition of the present invention. In the present specification, the organic solvent means a solvent having a vapor pressure of 1 atm or more at room temperature, that is, 101 kPa or more and capable of evaporating at room temperature.

As the organic solvent, a commercially available hydrocarbon solvent may be used. Specific examples of the organic solvent include olefin oligomers, ethylene-propylene oligomers, butene oligomers, 1-octene oligomers, 1-decene oligomers, 1-dodecene oligomers, and hydrides thereof. In addition, as an organic solvent, ketones such as acetone, ethyl methyl ketone and cyclohexanone, alcohols such as isopropyl alcohol, isobutyl alcohol, isopentyl alcohol and cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,4- Ethers such as dioxane, aromatics such as benzene, toluene and xylene, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, television oil, mineral oil, mineral spirit and the like may be adopted.

The proportion of the organic solvent in the rust preventive oil composition of the present invention can be exemplified in the range of 20 to 45% by mass and in the range of 25 to 40% by mass.

Known additives such as stabilizers and antifoaming agents can be added to the rust preventive oil composition of the present invention without departing from the spirit of the present invention. In the rust preventive oil composition of the present invention, the total ratio of the metal sulfonate, the fatty acid metal salt, the ester compound, the first base oil, the second base oil and the organic solvent is relative to the entire rust preventive oil composition of the present invention. , 98 to 100% by mass, more preferably 99 to 100% by mass, still more preferably 99.5 to 100% by mass.

An example of the method for producing the rust preventive oil composition of the present invention will be described. In a stirring mixer, three kinds of rust preventives, a first base oil and a second base oil are mixed and heated to obtain a solution in which three kinds of rust preventives are dissolved in the base oil. After cooling the solution, an organic solvent is added and further mixed to produce the rust preventive oil composition of the present invention.

Next, the iron product with an organic coating of the present invention will be described. The iron product with an organic film of the present invention is characterized by having an organic film formed by removing an organic solvent from the rust preventive oil composition of the present invention on the surface of the iron product coated with iron oxide.

Iron products mean products, intermediate products and parts made of steel. Typical examples of steel include carbon steel, alloy steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, and manganese steel. Carbon steels include low carbon steel with a carbon content of less than 0.3%, medium carbon steel with a carbon content of 0.3% to 0.7%, and high carbon steel with a carbon content of more than 0.7%. Can be exemplified.

In the iron product with an organic coating of the present invention, triiron tetroxide called black skin is present on the surface of the iron product body, and the organic coating is present on the surface of the black skin and / or the iron product body. Since the iron product body is coated with the black skin and the organic film, the occurrence of rust on the iron product body can be effectively suppressed due to the barrier functions of both. In the organic coating, the region where the ratio of the rust preventive agent is high, the region where the ratio of the first base oil is high, and the region where the ratio of the second base oil is high are in this order, the black skin and / or the surface side of the iron product body. It is presumed that they exist in order from.

The ratio of the rust preventive to the entire organic film is preferably 20 to 44% by mass.
When the ratio of metal sulfonate to the entire organic film is X _film mass%, the ratio of fatty acid metal salt is Y _film mass%, and the ratio of ester compound is Z _film mass%, X _film , Y _film and Z _film are as follows. It is preferable to satisfy all the conditions.
_{4 ≦ X film <20,4 ≦ Y} film <20,4 ≦ Z film <20,20 ≦ X film + Y film + Z film ≦ 44

The following conditions can be independently exemplified as preferable ranges of X _film , Y _film , and Z _film .
_{6 ≦ X film ≦ 19,6 ≦ X} film ≦ 13,9 ≦ X film ≦ 19,9 ≦ X film ≦ 13;
_{6 ≦ Y film ≦ 19,6 ≦ Y} film ≦ 13,9 ≦ Y film ≦ 19,9 ≦ Y film ≦ 13;
_{6 ≦ Z film ≦ 19,6 ≦ Z} film ≦ 13,9 ≦ Z film ≦ 19,9 ≦ Z film ≦ 13;
27 ≤ X _film + Y _film + Z _film ≤ 40, 30 ≤ X _film + Y _film + Z _film ≤ 37, 31 ≤ X _film + Y _film + Z _film ≤ 36

The ratio of the first base oil to the entire organic film is preferably in the range of 3 to 15% by mass, more preferably in the range of 3 to 10% by mass, further preferably in the range of 4 to 10% by mass, and 6 to 9%. The range of mass% is particularly preferable. The ratio of the second base oil to the entire organic film is preferably in the range of 41 to 74% by mass, more preferably in the range of 44 to 67% by mass, and further preferably in the range of 52 to 67% by mass.

The total of the ratio of the first base oil and the ratio of the second base oil to the entire organic coating is preferably in the range of 44 to 80% by mass, more preferably in the range of 56 to 78% by mass, and 59 to 76% by mass. The range of is more preferable. In the organic coating, the total ratio of the metal sulfonate, the fatty acid metal salt, the ester compound, the first base oil and the second base oil is preferably 98 to 100% by mass, preferably 99 to 100% by mass, based on the entire organic coating. More preferably, 99.5 to 100% by mass is further preferable.

An aspect of the method for producing an iron product with an organic coating of the present invention will be described.

The method for producing an iron product with an organic coating of the present invention is:
The first step of heat-treating the iron product body to austenite in a reducing atmosphere,
The second step, in which the iron product body after the first step is subjected to an oxygen atmosphere to form an iron oxide film on the surface of the iron product body,
The third step of cooling the iron product intermediate that has undergone the second step,
The fourth step of treating the iron product intermediate that has undergone the third step with the rust preventive oil composition of the present invention,
It is characterized by including.

The first step is a step of heat-treating the iron product body in a heating device for a certain period of time. By heat treatment, the entire iron product body becomes austenite. Since the iron product body is very easily oxidized during the heat treatment, the heat treatment is carried out in a reducing atmosphere filled with a reducing gas such as hydrogen or CH ₄ . Specific heating temperatures include the range of 800 to 1000 ° C.

The second step is a step of subjecting the iron product main body after the first step to an oxygen atmosphere to form an iron oxide film on the surface of the iron product main body. It is practically difficult to carry out all the steps from the first step to the third step in a reducing atmosphere or in a facility in which the atmosphere is shut off. Therefore, normally, the iron product main body is subjected to an oxygen atmosphere between the first step and the third step, and as a result, the surface of the iron product main body is oxidized to form an iron oxide film. It is formed.

The third step is a step of cooling the iron product intermediate that has undergone the second step. The third step corresponds to an austempering process, a marquenching process, a maltempered process, an aus forming process, and the like. The specific austempering process will be described below. The high-temperature iron product intermediate that has undergone the second step is rapidly cooled by putting it into a molten salt bath at 230 to 500 ° C., and the temperature is maintained for a certain period of time. By this austenite treatment, the austenite of the iron product body is converted into bainite. Examples of the salt used as the molten salt include sodium nitrate, potassium nitrate, barium nitrate, sodium nitrite, potassium nitrite, barium nitrite, sodium chloride, potassium chloride, barium chloride, and mixtures thereof. After the austempering treatment, washing with water is performed to remove salts from the iron product intermediates.

The fourth step is a step of treating the iron product intermediate that has undergone the third step with the rust preventive oil composition of the present invention. Specific treatment methods include a method of immersing the iron product intermediate in the rust preventive oil composition of the present invention, a method of spraying the rust preventive oil composition of the present invention on the iron product intermediate, and the present invention on the iron product intermediate. An example of a method of applying the rust preventive oil composition of. Then, the organic solvent is removed from the rust preventive oil composition of the present invention that coats the iron product intermediate to form an organic film. The method for removing the organic solvent may be a method of leaving at room temperature, a method of drying under heating and / or reduced pressure conditions, or a method of spraying a dry gas.

In the iron product with an organic coating of the present invention, rust is generated due to the presence of black skin and an organic coating containing a specific ratio of three types of rust preventives and a specific type of base oil. Effectively suppressed.

Hereinafter, the present invention will be described in more detail through examples. These examples are for more specific explanation of the present invention, and the scope of the present invention is not limited to these examples. It can be carried out in various forms with modifications, improvements, etc. that can be made by those skilled in the art, without departing from the gist of the present invention.

(Example 1)
As rust preventives, mineral oil sulfonic acid barium salt which is a metal sulfonate, lanolin fatty acid calcium salt which is a fatty acid metal salt, and lanolin fatty acid ester which is an ester compound were prepared. Further, a mineral oil having a kinematic viscosity of 9 mm ² / s at 40 ° C. was prepared as the first base oil, and a mineral oil having a kinematic viscosity of 500 mm ² / s at 40 ° C. was prepared as the second base oil. Further, as an organic solvent, a mineral oil having a vapor pressure of 1 atm or more at room temperature was prepared.

7.5 parts by mass of metal sulfonate, 7.5 parts by mass of fatty acid metal salt, 7.5 parts by mass of ester compound, 5.5 parts by mass of first base oil and 44.5 parts by mass of second base oil are mixed to prevent rust. The mixture was heated until the agent was dissolved. The mixture was cooled and 27.5 parts by mass of an organic solvent was added to obtain a rust preventive oil composition of Example 1.

The iron product body was heated at 850 ° C. for 20 minutes in a non-oxidizing atmosphere. The iron product body after heating was passed through the atmosphere, put into sodium nitrite salt at 330 ° C., and cooled for 40 minutes (austemper treatment). Then, it was washed with water to obtain an iron product intermediate whose surface was coated with iron oxide. The surface of the iron product body was coated with iron oxide because the surface of the iron product body came into contact with oxygen in the atmosphere while passing through the atmosphere after heating at 850 ° C.

The iron product intermediate whose surface was coated with iron oxide was immersed in the rust preventive oil composition of Example 1. The iron product intermediate was taken out from the rust preventive oil composition of Example 1 and allowed to stand to dry at room temperature to volatilize and remove the organic solvent from the rust preventive oil composition adhering to the iron product intermediate. An iron product with an organic coating of Example 1 was produced by such a procedure.

(Example 2)
Anti-corrosion of Example 2 in the same manner as in Example 1 except that 4.5 parts by mass of the first base oil, 35.5 parts by mass of the second base oil, and 37.5 parts by mass of the organic solvent were used. An oil composition and an iron product with an organic coating of Example 2 were produced.

(Example 3)
The rust preventive oil composition of Example 3 and the embodiment were carried out in the same manner as in Example 2 except that 5 parts by mass of the metal sulfonate, 5 parts by mass of the fatty acid metal salt and 12.5 parts by mass of the ester compound were used. An iron product with an organic coating of Example 3 was produced.

(Example 4)
The rust preventive oil composition of Example 4 and the embodiment were carried out in the same manner as in Example 2 except that 12.5 parts by mass of metal sulfonate, 5 parts by mass of fatty acid metal salt and 5 parts by mass of ester compound were used. An iron product with an organic coating of Example 4 was produced.

(Example 5)
The rust preventive oil composition of Example 5 and the embodiment were carried out in the same manner as in Example 2 except that 5 parts by mass of metal sulfonate, 12.5 parts by mass of fatty acid metal salt and 5 parts by mass of ester compound were used. An iron product with an organic coating of Example 5 was produced.

(Example 6)
The same method as in Example 1 was carried out except that 4.5 parts by mass of mineral oil having a kinematic viscosity of 5 mm ² / s at 40 ° C. was used as the first base oil and 45.5 parts by mass of the second base oil. The rust preventive oil composition of Example 6 and the iron product with an organic coating of Example 6 were produced.

(Example 7)
The rust prevention of Example 7 was carried out in the same manner as in Example 6 except that 3.5 parts by mass of the first base oil, 36.5 parts by mass of the second base oil and 37.5 parts by mass of the organic solvent were used. An oil composition and an iron product with an organic coating of Example 7 were produced.

(Example 8)
Except for using 9 parts by mass of mineral oil with a kinematic viscosity of 46 mm ² / s at 40 ° C as the first base oil and 41.0 parts by mass of mineral oil with a kinematic viscosity of 430 mm ² / s at 40 ° C as the second base oil. Produced the rust-preventive oil composition of Example 8 and the iron product with an organic coating of Example 8 in the same manner as in Example 1.

(Example 9)
The rust preventive oil composition of Example 9 was carried out in the same manner as in Example 8 except that 7 parts by mass of the first base oil, 33.0 parts by mass of the second base oil and 37.5 parts by mass of the organic solvent were used. A product and an iron product with an organic coating of Example 9 were produced.

(Comparative Example 1)
The same method as in Example 1 was used except that 13 parts by mass of mineral oil having a kinematic viscosity of 100 mm ² / s at 40 ° C. and 37.0 parts by mass of mineral oil having a kinematic viscosity of 380 mm ² / s at 40 ° C. were used. , The rust-preventive oil composition of Comparative Example 1 and the iron product with an organic coating of Comparative Example 1 were produced.

(Comparative Example 2)
10.5 parts by mass of mineral oil having a kinematic viscosity of 100 mm ² / s at 40 ° C., 29.5 parts by mass of mineral oil having an kinematic viscosity of 380 mm ² / s at 40 ° C., and 37.5 parts by mass of an organic solvent were used. Except for the above, the rust-preventive oil composition of Comparative Example 2 and the iron product with an organic coating of Comparative Example 2 were produced in the same manner as in Comparative Example 1.

(Comparative Example 3)
5 parts by mass of mineral oil with a kinematic viscosity of 9 mm ² / s at 40 ° C as the first base oil, and 41.0 parts by mass of mineral oil with a kinematic viscosity of 500 mm ² / s at 40 ° C as the second base oil. The rust-preventive oil composition of Comparative Example 3 and the organic of Comparative Example 3 were used in the same manner as in Example 1 except that 22.5 parts by mass of metal sulfonate was used and no fatty acid metal salt and ester compound were used. Manufactured coated iron products.

(Comparative Example 4)
Same as in Example 1 except that 5 parts by mass of the first base oil, 41.0 parts by mass of the second base oil, and 22.5 parts by mass of the fatty acid metal salt were used, and no metal sulfonate and ester compound were used. When the rust preventive oil composition of Comparative Example 4 was produced by the method, the rust preventive oil composition of Comparative Example 4 was gelled. Therefore, the iron product with an organic coating of Comparative Example 4 was not manufactured.

(Comparative Example 5)
Same as in Example 1 except that 5 parts by mass of the first base oil, 41.0 parts by mass of the second base oil, and 22.5 parts by mass of the ester compound were used, and no metal sulfonate and fatty acid metal salt were used. By the method, the rust preventive oil composition of Comparative Example 5 and the iron product with an organic coating of Comparative Example 5 were produced.

(Reference Examples 1 to 9, Reference Comparative Examples 1 to 5)
An iron product whose surface was not coated with iron oxide, that is, an iron product which had not been heat-treated or austempered, was immersed in the rust preventive oil composition of Examples 1 to 9 or Comparative Examples 1 to 5. The iron product is taken out from the rust preventive oil composition of Examples 1 to 9 or Comparative Examples 1 to 5 and allowed to stand and dry at room temperature to volatilize an organic solvent from the rust preventive oil composition adhering to the iron product. Removed. By such a procedure, iron products with an organic coating of Reference Examples 1 to 9 or Reference Comparative Examples 1 to 5 corresponding to Examples 1 to 9 or Comparative Examples 1 to 5 were produced.

(Evaluation 1)
In the JIS Z 2371 salt spray test method, the iron products with an organic coating of Examples 1 to 9 or Comparative Examples 1 to 5 and the iron products with an organic coating of Reference Examples 1 to 9 or Reference Comparative Examples 1 to 5 were used. A neutral salt spray test was performed in which a 5% NaCl solution was sprayed. Each iron product with an organic film was visually observed, and the time during which red rust occurred was measured. The results are shown in Table 1 together with a list of rust preventive oil compositions of Examples 1-9 or Comparative Examples 1-5. The kinematic viscosity in the table is a value measured by the kinematic viscosity test method described in JIS K 2283.

From the results in Table 1, it can be seen that in the iron products with an organic coating of Examples 1 to 9, no red rust was observed for at least 600 hours. Further, it can be seen that the iron products with an organic coating of Examples 1 to 9 were able to extend the red rust generation time by 100 hours or more as compared with the iron products with an organic coating of Reference Examples 1 to 9. It can be said that the rust-preventive oil composition of the present invention effectively exerts a rust-preventive effect particularly on iron products coated with iron oxide. The red rust generation time of the iron products of Examples 1 to 7 in which the first base oil has a lower viscosity exceeds 800 hours, which is particularly preferable.

Further, from the results of Examples 1 and 2 and Examples 3 to 5 and Comparative Examples 3 to 5, the rust preventive effect can be obtained by using three kinds of rust preventive agents of metal sulfonate, fatty acid metal salt and ester compound in combination. It turns out that it becomes remarkably remarkable. From the above results, it was confirmed that the rust preventive oil composition of the present invention and the iron product with an organic coating of the present invention are excellent.

(Evaluation 2)
The aniline point of each base oil was measured by the test method described in JIS K 2256. The results are shown in Table 2.

Considering this together with the result of Evaluation 1, the aniline point of the first base oil is particularly preferably in the range of 75 to 85 ° C, and the aniline point of the second base oil is particularly preferably in the range of 130 to 140 ° C. The aniline point of the entire base oil, which is a mixture of the first base oil and the second base oil, is particularly preferably in the range of 115 to 120 ° C.

(Evaluation 3)
The mixed oil in which the first base oil and the second base oil were mixed at the ratio specified in the rust preventive oil composition of the present invention was analyzed under the following GPC conditions. The obtained chromatogram is shown in FIG. In the chromatogram of FIG. 1, a peak derived from the first base oil and a peak derived from the second base oil were observed in a state of being separated from each other. It was confirmed that the second base oil having a large molecular weight was eluted first, and the first base oil having a small molecular weight was eluted later. For identification of each peak in the chromatogram of FIG. 1, each of the first base oil and the second base oil was analyzed under the same GPC conditions, and the retention time (elution) of the first base oil and the second base oil was performed. I went by means of confirming the time).

<GPC conditions>
Column: Shodex GPC KF-801, KF-802 and KF-802.5 are connected (all by Showa Denko KK)
Mobile phase: Tetrahydrofuran Flow rate: 1 mL / min.
Detector: UV photometer

Claims (10)

A rust preventive containing a metal sulfonate, a fatty acid metal salt and an ester compound, a first base oil having a kinematic viscosity at 40 ° C. of 3 to 20 mm ² / s, and a kinematic viscosity at 40 ° C. of 300 to 600 mm ² A rust preventive oil composition containing a second base oil having / s and an organic solvent.
The ratio of the rust preventive agent to the entire rust preventive oil composition is 15 to 30% by mass, the ratio of the first base oil is 2 to 10% by mass, and the ratio of the second base oil is 28 to 50% by mass. A rust preventive oil composition for iron products coated with iron oxide, which is characterized by being. When the ratio of the metal sulfonate to the entire rust preventive oil composition is X% by mass, the ratio of the fatty acid metal salt is Y% by mass, and the ratio of the ester compound is Z% by mass, X, Y and Z are all the following conditions. The rust preventive oil composition according to claim 1.
3 ≦ X <15, 3 ≦ Y <15, 3 ≦ Z <15, 15 ≦ X + Y + Z ≦ 30 The rust preventive oil composition according to claim 1 or 2, wherein the second base oil has a kinematic viscosity of 430 to 600 mm ² / s at 40 ° C. (Rust generation time of iron products not coated with iron oxide treated with the rust preventive oil composition) (Rust generation time of iron products coated with iron oxide treated with the rust preventive oil composition) The rust preventive oil composition according to any one of claims 1 to 3, wherein the ratio of is 1 or more. In any one of claims 1 to 4, in which the peak derived from the first base oil and the peak derived from the second base oil are observed in the analysis chart for measuring the molecular weight distribution of the rust preventive oil composition. The rust preventive oil composition described. An iron product with an organic coating coated with iron oxide and an organic coating.
An iron product with an organic coating, wherein the organic coating is formed by removing an organic solvent from the rust preventive oil composition according to any one of claims 1 to 5. An iron product with an organic coating coated with iron oxide and an organic coating.
The organic coating contains a rust preventive containing a metal sulfonate, a fatty acid metal salt and an ester compound, a first base oil having a kinematic viscosity of 3 to 20 mm ² / s at 40 ° C, and a kinematic viscosity at 40 ° C. Includes a second base oil of 300-600 mm ² / s
Moreover, the ratio of the rust preventive agent is 20 to 44% by mass, the ratio of the first base oil is 3 to 15% by mass, and the ratio of the second base oil is 41 to 74% by mass with respect to the entire organic coating. An iron product with an organic coating, which is characterized by being. The iron product with an organic coating according to claim 6 or 7, wherein a peak derived from the first base oil and a peak derived from the second base oil are observed in the analysis chart for measuring the molecular weight distribution of the organic coating. The method for producing an iron product with an organic coating according to any one of claims 6 to 8.
The first step of heat-treating the iron product body to austenite in a reducing atmosphere,
The second step, in which the iron product body after the first step is subjected to an oxygen atmosphere to form an iron oxide film on the surface of the iron product body,
The third step of cooling the iron product intermediate that has undergone the second step,
A method for producing an iron product with an organic coating, which comprises a fourth step of treating the iron product intermediate that has undergone the third step with the rust preventive oil composition according to any one of claims 1 to 5. A method for manufacturing an iron product with an organic coating coated with iron oxide and an organic coating.
The organic film is formed by removing the organic solvent from the rust preventive oil composition.
The rust preventive oil composition contains a rust preventive agent containing a metal sulfonate, a fatty acid metal salt and an ester compound, and has a kinematic viscosity of 2 to 50 mm at 40 ° C. ² The first base oil with / s and the kinematic viscosity at 40 ° C. are 300 to 600 mm. ² It contains a second base oil of / s and an organic solvent, and the ratio of the rust preventive agent to the entire rust preventive oil composition is 15 to 30% by mass, and the ratio of the first base oil is 2. The ratio of the second base oil is 10 to 10% by mass, and the ratio of the second base oil is 28 to 50% by mass.
The first step of heat-treating the iron product body to austenite in a reducing atmosphere,
The second step, in which the iron product body after the first step is subjected to an oxygen atmosphere to form an iron oxide film on the surface of the iron product body,
The third step of cooling the iron product intermediate that has undergone the second step,
A method for producing an iron product with an organic coating, which comprises a fourth step of treating an iron product intermediate that has undergone the third step with the rust preventive oil composition.