JP5366416B2 - Rust prevention oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem of a conventional rust-preventive oil composition, which may cause trouble of rust formation because of its insufficient performance of a neutral salt water spray test (JIS K2246) though it requires no degreasing by a solvent to reduce bad influence to heat treatment. <P>SOLUTION: The rust-preventive oil composition with kinematic viscosity of 1-100 mm<SP>2</SP>/s at 40&deg;C is provided when an alcohol derivative of amine represented by a formula (1) is blended in a base oil by an amount of 0.5-25 mass% based on the total amount of the composition. In the formula (1), R<SP>1</SP>is an 8-24C hydrocarbon group which may be a straight/branched chain or a saturated/unsaturated group; and R<SP>2</SP>and R<SP>3</SP>may be the same with or different from each other and are each a 1-12C hydrocarbon group which may be a straight/branched chain or a saturated/unsaturated group. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a rust-preventing oil composition, and particularly to a rust-preventing oil composition that exhibits good performance for metal parts subjected to heat treatment.

Conventionally, rust preventive oils used for rust prevention of metal parts include sulfonic acid metal salts, wax oxide esters, wax oxide metal salts, petrolatum, waxes, etc. as rust inhibitors. Or they were used in combination, but when heat-treating metal parts with these rust inhibitors, some of the metal parts after hardening were darkened, and the hardness was insufficient. Occurrence of parts, occurrence of parts that are not nitrided by nitriding and quenching, and parts of poor carburizing by carburizing and quenching may occur.
For this reason, when heat treating metal parts with rust preventive agent attached, it was necessary to degrease them thoroughly using a solvent to remove rust preventive oil. It has been desired to avoid the use of hydrogen solvents as much as possible. As a result, an ashless rust-preventing oil that contains no metal and contains rust inhibitors such as organic acid amine salts and polyhydric alcohol partial esters has been developed, eliminating the need for solvent degreasing and suppressing adverse effects on heat treatment. A rust preventive oil composition has been developed (see Patent Document 1).

However, these conventional rust-preventing oils have insufficient performance in the neutral salt spray test (JIS K2246) for evaluating rust-preventing performance in overseas transportation of metal parts and use in the vicinity of the coast. , May cause rusting trouble.
JP 2000-265189 A

  Therefore, the present invention has been made in view of such a situation, and its purpose is to eliminate or simplify the degreasing treatment with a solvent such as hydrocarbon, minimizing adverse effects on heat treatment, Another object of the present invention is to provide a rust preventive oil composition having sufficient performance in a neutral salt spray test (JIS K2246).

  As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a rust-preventing oil having a specific composition enables simplification of degreasing treatment with a solvent such as hydrocarbon, and metal The present inventors have found that it is excellent in rust prevention properties for manufactured parts, and completed the present invention.

（式（１）中、Ｒ^１は炭素数８〜２４の炭化水素基であり、直鎖又は分岐鎖でもよく、飽和又は不飽和でもよい。Ｒ^２及びＲ^３は、それぞれ同一でも異なっていてもよく、炭素数１〜１２の炭化水素基であり、直鎖又は分岐鎖でもよく、飽和又は不飽和でもよい。）
また、金属元素の総含有量が組成物全量基準で０．１質量％未満である前記のさび止め油組成物に関する。 That is, in the present application, at least one selected from (A) mineral oil and / or synthetic oil is used as a base oil, and (B) an alcohol derivative of amine represented by the formula (1) based on the total amount of the composition is 0.00. The present invention relates to a rust preventive oil composition containing 5 to 25% by mass and having a kinematic viscosity at 40 ° C. of 1 to 100 mm ² / s.

(In the formula (1), R ¹ is a hydrocarbon group having 8 to 24 carbon atoms, which may be linear or branched, and may be saturated or unsaturated. R ² and R ³ may be the same or different. Or a hydrocarbon group having 1 to 12 carbon atoms, which may be linear or branched, and may be saturated or unsaturated.)
The present invention also relates to the rust preventive oil composition, wherein the total content of metal elements is less than 0.1% by mass based on the total composition.

  As described above, according to the present invention, by blending a specific rust inhibitor, it has good rust prevention performance for metal parts subjected to heat treatment, and some of the metal parts after heat treatment are It becomes possible to provide a rust-preventing oil composition that does not cause the appearance of poor appearance such as blackening, the occurrence of insufficient hardness, the occurrence of non-nitriding by nitriding and quenching, and the occurrence of poor carburizing by carburizing and quenching. .

The rust preventive oil composition of the present invention includes a base oil composed of mineral oil and / or synthetic oil.
Specifically, as mineral oils, solvent degreasing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogen removal from lubricating oil fractions obtained by atmospheric and vacuum distillation of crude oil Examples thereof include paraffinic or naphthenic mineral oil obtained by appropriately combining one or more purification means of chemical purification, sulfuric acid washing, and clay treatment.

  Moreover, polyolefin, alkylbenzene, etc. are used suitably as synthetic oil.

  Examples of the polyolefin include those obtained by homopolymerization or copolymerization of olefin monomers having 2 to 16 carbon atoms, preferably 2 to 12 carbon atoms, and hydrides of these polymers. In the case where the polyolefin is a copolymer of olefin monomers having different structures, the monomer ratio and the monomer arrangement in the copolymer are not particularly limited, and among random copolymers, alternating copolymers and block copolymers. Any of these may be used. The olefin monomer may be any of α-olefin, internal olefin, linear olefin, and branched olefin. Specific examples of such olefin monomers include ethylene, propylene, 1-butene, 2-butene, isobutene, linear or branched pentene (including α-olefin and internal olefin), linear Or branched hexene (including α-olefin and internal olefin), linear or branched heptene (including α-olefin and internal olefin), linear or branched octene (α-olefin) ), Linear or branched nonene (α-olefin, including internal olefin), linear or branched decene (including α-olefin, internal olefin), linear Alternatively, branched undecene (including α-olefin and internal olefin), linear or branched dodecene (including α-olefin and internal olefin), linear Or branched tridecene (including α-olefin and internal olefin), linear or branched tetradecene (including α-olefin and internal olefin), linear or branched pentadecene (α-olefin) ), Linear or branched hexadecene (α-olefin, including internal olefin), and mixtures thereof. Among these, ethylene, propylene, 1-butene, 2- Butene, isobutene, an α-olefin having 5 to 12 carbon atoms and a mixture thereof are preferably used. Further, among the α-olefins having 5 to 12 carbon atoms, 1-octene, 1-decene, 1-dodecene, a mixture thereof, and the like are more preferable.

  The above-described polyolefin can be produced by a conventionally known method. Polyolefins obtained by conventionally known methods usually have double bonds, but in the present invention, so-called polyolefin hydrides obtained by hydrogenating double bond carbons in these polyolefins are used as base oils. It is preferable. When a hydride of polyolefin is used, the thermal / oxidative stability of the obtained rust preventive oil composition tends to be improved. The polyolefin hydride can be obtained, for example, by hydrogenating a polyolefin in the presence of a known hydrogenation catalyst and saturating double bonds present in the polyolefin. In addition, when the olefin polymerization reaction is performed, by selecting the catalyst to be used, the olefin polymerization and the double bond existing in the polymer can be performed without passing through two steps such as olefin polymerization and polymer hydrogenation. It is also possible to complete the hydrogenation in one step.

  Among the polyolefins preferably used as a base oil in the present invention, an ethylene-propylene copolymer, polybutene (butane-butene fraction (by-product of 1-butene, 2-butene and A copolymer obtained by polymerization of a mixture of isobutene), 1-octene oligomer, 1-decene oligomer, 1-dodecene oligomer and their hydrides, and also a mixture thereof are heat / oxidative stability, viscosity- Preferred in terms of excellent temperature characteristics and low temperature fluidity, especially ethylene-propylene copolymer hydride, polybutene hydride, 1-octene oligomer hydride, 1-decene oligomer hydride, 1-dodecene oligomer hydride and These mixtures are more preferred. Synthetic oils such as ethylene-propylene copolymers, polybutenes, and poly-α-olefins that are commercially available as base oils for lubricants are usually those whose double bonds are already hydrogenated. In the invention, these commercially available products can also be used as the base oil.

  Moreover, as an alkylbenzene used suitably as a base oil concerning this invention, what has 1-4 C1-C40 alkyl groups in a molecule | numerator is preferable. Specific examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group (including all isomers), a butyl group (including all isomers), and a pentyl group ( All isomers included, hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) ), Decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers), tetradecyl group (all ), Pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octadecyl group (including all isomers) ), Nonadecyl group (including all isomers), icosyl group (including all isomers), heicosyl group (including all isomers), docosyl group (including all isomers), tricosyl group (all ), Tetracosyl group (including all isomers), pentacosyl group (including all isomers), hexacosyl group (including all isomers), heptacosyl group (including all isomers) , Octacosyl group (including all isomers), nonacosyl group (including all isomers), triacontyl group (including all isomers), hentriacontyl group (including all isomers), dotriacontyl group ( All isomers), tritriacontyl group (including all isomers), tetratriacontyl group (including all isomers), pentato Acontyl group (including all isomers), hexatriacontyl group (including all isomers), heptatriacontyl group (including all isomers), octatriacontyl group (including all isomers) ), Nonatoriacontyl group (including all isomers), tetracontyl group (including all isomers), and the like. Further, the alkyl group of the alkylbenzene according to the present invention may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and particularly easily available. In view of the above, branched alkyl groups derived from olefin oligomers such as propylene, butene and isobutylene are more preferred.

  The number of alkyl groups in the alkylbenzene used in the present invention is preferably 1 to 4, but from the viewpoints of stability and availability, alkylbenzene having one or two alkyl groups, that is, monoalkylbenzene, dialkylbenzene, Or a mixture thereof is most preferred. Moreover, as alkylbenzene, not only the alkylbenzene of a single structure but the mixture of the alkylbenzene which has a different structure may be sufficient.

In the present invention, the kinematic viscosities of the various base oils at 40 ° C. are usually selected from the range of 1 to 1000 mm ² / s, preferably ² to 100 mm ² / s, more preferably 3 to 95 mm ² / s. A base oil may be used individually by 1 type, and 2 or more types of base oils may be mixed and used for it. In the rust preventive oil composition of the present invention, a heavy base oil having a kinematic viscosity at 40 ° C. of 100 mm ² / s or more, for example, 100 to 1000 mm ² / s, preferably 200 to 500 mm ² / s. The content of the heavy group is not particularly limited, but from the viewpoint of optimizing the thickening of the coating film of the rust preventive oil composition in the present invention, the suppression of the increase in the amount taken out, and the degreasing and spraying properties. The oil content is preferably 1 to 40% by mass, more preferably 5 to 15% by mass, based on the total amount of the composition.

  Furthermore, the content of the base oil of the rust prevention oil composition in the present invention is not particularly limited and is arbitrary, but the lower limit value of the base oil relative to the composition is 50% by mass, preferably 70% by mass, more preferably 80% by weight, most preferably 90% by weight.

式（１）中、Ｒ^１は優れたさび止め性能が得られることから、１，１−ジメチルヘキシル基、１，１−ジメチルオクチル基、１，１−ジメチルノニル基、１，１−ジメチルデシル基、１，１−ジメチルウンデシル基、１，１−ジメチルドデシル基、１，１−ジメチルトリデシル基、１，１−ジメチルテトラデシル基、１，１−ジメチルペンタデシル基、１，１−ジメチルヘキサデシル基、１，１−ジメチルヘプタデシル基１，１−ジメチルオクタデシル基、１，１−ジメチルノナデシル基、１，１−ジメチルエイコシル基が好ましく、１，１−ジメチルドデシル基、１，１−ジメチルトリデシル基、１，１−ジメチルテトラデシル基、１，１−ジメチルペンタデシル基、１，１−ジメチルヘキサデシル基、１，１−ジメチルヘプタデシル基１，１−ジメチルオクタデシル基である。 The rust preventive oil composition of the present invention contains 0.5 to 25% by mass of an alcohol derivative of an amine represented by the formula (1) as an essential component (B) based on the total amount of the composition.

In the formula (1), R ¹ has excellent rust prevention performance , so that 1,1-dimethylhexyl group, 1,1-dimethyloctyl group, 1,1-dimethylnonyl group, 1,1-dimethyldecyl Group, 1,1-dimethylundecyl group, 1,1-dimethyldodecyl group, 1,1-dimethyltridecyl group, 1,1-dimethyltetradecyl group, 1,1-dimethylpentadecyl group, 1,1- Dimethylhexadecyl group, 1,1-dimethylheptadecyl group, 1,1-dimethyloctadecyl group, 1,1-dimethylnonadecyl group, 1,1-dimethyleicosyl group are preferable, 1,1-dimethyldodecyl group, , 1-dimethyltridecyl group, 1,1-dimethyltetradecyl group, 1,1-dimethylpentadecyl group, 1,1-dimethylhexadecyl group, 1,1-dimethylheptadecyl group , 1-dimethyl octadecyl group.

R ² and R ³ may be the same or different and are each a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, more preferably 2 To 4 divalent hydrocarbon groups, which may be linear or branched, saturated or unsaturated, but are preferably linear or branched alkylene groups. Specifically, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and the like can be mentioned because excellent rust prevention performance can be obtained.

Specific examples of the anticorrosive additive for component (B) include the following.

B1: Alkylamine alcohol derivative represented by the following formula (2).
B2: Alkylamine alcohol derivative represented by the following formula (3).
B3: Alcohol derivative of alkylamine represented by the following formula (4).
B4: Alcohol derivative of alkylamine represented by the following formula (5).
B5: Alkylamine alcohol derivative represented by the following formula (6).
B6: Alcohol derivative of alkylamine represented by the following formula (7).

The upper limit of the content of the component (B) in the rust preventive oil composition of the present invention is 25% by mass, preferably 20% by mass, more preferably 15% by mass, based on the total amount of the composition. When the content exceeds 25% by mass, the cost efficiency and storage stability are deteriorated, which is not preferable.
On the other hand, the lower limit of the content of the component (B) is 0.05% by mass, preferably 1% by mass, more preferably 2% by mass, based on the total amount of the composition. When the content of the component (B) is less than 0.05% by mass, the rust prevention effect is insufficient, which is not preferable.

  Further, the rust-preventing oil composition of the present invention is further required to have a total content of metal elements of less than 0.1% by mass, preferably less than 0.05% by mass, based on the total amount of the composition. Problems caused by heat treatment can be prevented. In the present invention, the content of the metal element means ASTM D5185-95 “Standard Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic Emission. It means the content of the metal element based on the total amount of the composition measured according to “Spectrometry (ICP-AES)”.

The kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is required to be 1 to 100 mm ² / s. From the viewpoint of corrosion resistance, the lower limit value, 1 mm ² / or more, preferably ^{3 mm} 2 / s or more, more preferably it is desirable that the ^{5 mm} 2 / s or more. Further, from the viewpoints of handleability and adhesion amount, the upper limit value is desirably 100 mm ² / s or less, preferably 75 mm ² / s or less, and more preferably 50 mm ² / s or less.

  In addition, to the rust preventive oil composition of the present invention, other known additives can be added alone or in combination of several kinds for the purpose of further enhancing the performance. Specific examples of these additives include the above-mentioned alcohols such as oxidized wax salts, carboxylic acids, sulfonates, carboxylates, esters, sarcosine, amines, boron compounds, higher aliphatic alcohols, and the like. Anti-rust additive other than component (B); film forming agent such as paraffin wax, microwax, slack wax, polyolefin wax, petrolatum, etc., which has a remarkable effect of improving the anti-corrosion property in an acidic atmosphere; Represented by phosphoric acid esters, phosphoric acid esters, phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid esters, and their amine salts such as sulfurized fats and oils, sulfurized esters, long-chain alkyl zinc dithiophosphates, tricresyl phosphates, etc. (Sub) phosphoric acid derivatives; fats and oils such as pork fat, fatty acids, high grade Lubricant improvers typified by rucol, etc .; calcium carbonate, potassium borate; phenol-based or amine-based antioxidants for improving the antioxidant performance; corrosion inhibitors (benzotriazole or Derivatives thereof, thiadiazole, benzothiazole, etc.); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers; antifoaming agents such as methyl silicone, fluorosilicone, polyacrylate; water and surface activity for removing water-soluble spoilage factors Agents, mixtures thereof, and the like, and these may be used alone or in combination of two or more. The content when these known additives are used in combination is arbitrary, but it is usually desirable to add such an amount that the total content of these known additives is 10% by mass or less based on the total amount of the composition. . In addition, when using the rust preventive oil composition of the present invention for metal parts subjected to heat treatment, it is natural to select an additive that does not affect the heat treatment when selecting the additive. There must be.

  As the oxidized wax salt, an oxidized wax obtained by oxidizing a wax and at least one selected from an alkali metal, an alkaline earth metal (excluding barium) and an amine are reacted to produce an oxidized wax. A salt obtained by neutralizing some or all of the acidic groups is preferred.

  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.

  Examples of the monoamine include alkylamines, alkenylamines, monoamines having an alkyl group and an alkenyl group, aromatic substituted alkylamines, alkylcycloalkylamines, and the like. The monoamine referred to here includes monoamines derived from fats and oils (such as beef tallow amine).

  Examples of polyamines include alkylene polyamines, N-alkylethylenediamines, N-alkenylethylenediamines, N-alkyl or N-alkenylalkylenepolyamines, and the like. The polyamine referred to here also includes polyamines derived from fats and oils (such as beef tallow polyamine).

  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.

  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, but from the point of rust prevention 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 is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more based on the total amount of the composition from the viewpoint of rust prevention. It is. 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.

  Any carboxylic acid can be used, and preferred examples include fatty acids, dicarboxylic acids, hydroxy fatty acids, naphthenic acids, resin acids, oxidized waxes, and lanolin fatty acids.

  Although carbon number in particular of a fatty acid is not restrict | limited, Preferably it is 6-24, More preferably, it is 10-22. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched chain fatty acid.

  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 the carboxylic acid is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.05% by mass or more based on the total amount of the composition. 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. .

  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, the conventionally well-known thing manufactured by the conventional method can be used for a sulfonic acid. Specifically, the sulfonated alkyl aromatic compound of the lubricating oil fraction of mineral oil, the petroleum sulfonic acid such as mahogany acid produced as a by-product during white oil production, the sulfonated alkylbenzene, dinonyl naphthalene, etc. And synthetic sulfonic acids such as those obtained by sulfonating alkyl naphthalene. 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, it is preferable to use at least one selected from the group consisting of dialkylnaphthalenesulfonic acid, dialkylbenzenesulfonic acid, and monoalkylbenzenesulfonic acid.

  The dialkyl naphthalene sulfonic acid preferably has a total carbon number of 14 to 30 of two alkyl groups bonded to the naphthalene ring. 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.

  In addition, dialkylbenzenesulfonic acid 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, monoalkylbenzenesulfonic acid is one in which one alkyl group bonded to the benzene ring has 15 or more carbon atoms. 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, an alkali metal base (alkali metal oxide or hydroxide, etc.), an alkaline earth metal base (alkali earth metal oxide or hydroxide, etc.) or an amine (ammonia, alkylamine, alkanolamine, etc.) ) And a sulfonic acid to obtain a neutral (normal salt) sulfonate; the above 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. Basic sulfonates obtained by heating under; carbonates obtained by reacting the above neutral (normal salt) sulfonates with alkali metal bases, alkaline earth metal bases or amines in the presence of carbon dioxide Overbasic (superbasic) sulfonates; neutral (normal salt) sulfonates described above may be converted to alkali metal bases, alkaline earth metal bases or amino acids. Boric acid obtained by reaction with boric acid compounds such as boric acid or boric anhydride, or by reacting the above carbonate overbased (superbasic) sulfonates with boric acid compounds such as boric acid or boric anhydride Examples include salt overbased (superbasic) sulfonates, and mixtures thereof.

  The chlorine concentration in the sulfonate is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, and particularly preferably 25 ppm by mass or less. preferable.

  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 esters include partial esters of polyhydric alcohols, esterified oxidized waxes, esterified lanolin fatty acids, alkyl or alkenyl succinates.

  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. Further, the carboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, may be a linear carboxylic acid or a branched carboxylic acid, and a mixture thereof. There may be.

  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).

In the formula, 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.

In the formula, 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.

  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. 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.

As sarcosine, a compound represented by any one of the following general formulas (3) to (5) is preferably used. By including the sarcosine represented by the general formulas (3) to (5) in the rust preventive oil composition of the present invention, rust preventive properties can be obtained without using heavy components such as wax, petrolatum, and heavy base oil. In addition, the anti-corrosion property can be maintained at a high level over a long period of time, so that the anti-corrosion property and the long-term maintainability are excellent, and the increase in the amount taken out is suppressed and the degreasing is performed. It is possible to obtain a rust-preventing oil composition advantageous in terms of water and sprayability.

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. The alkyl group may be linear or branched, and the alkenyl group may be linear or branched, and the position of the double bond is arbitrary.

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. The alkyl group may be linear or branched, and the alkenyl group 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 represented by the general formulas (3) to (5), the sarcosine is at least one compound selected from the general formulas (3) and (4) from the viewpoint of more excellent anti-rust properties. 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.

  In producing the above rust inhibitor, a chlorine bleach may be used for the purpose of decolorization. In the present invention, a specific chlorine compound such as hydrogen peroxide is used as a bleach. Alternatively, it is preferable not to perform the decoloring process. In addition, chlorine compounds such as hydrochloric acid may be used for the hydrolysis of fats and oils. In this case, it is also preferable to use a non-chlorine acid or basic compound. Furthermore, it is preferable to subject the resulting compound to a sufficient washing treatment such as washing with water.

  Further, the chlorine concentration of the rust preventive additive is not particularly limited as long as the characteristics of the rust preventive oil composition are not impaired, but is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less. Yes, more preferably 50 ppm or less, particularly preferably 25 ppm by mass or less.

  Further, in the rust preventive oil composition of the present invention, the barium, zinc, chlorine and lead contents are each in terms of elements, and based on the total amount of the rust preventive oil composition, 1000 ppm by mass or less, more preferably 500 ppm by mass Hereinafter, more preferably 100 ppm by mass or less, still more preferably 50 ppm by mass or less, still more preferably 10 ppm by mass or less, particularly preferably 5 ppm by mass or less, and most preferably 1 ppm by mass or less. If the content of any one of these elements exceeds 1000 ppm by mass, there is a possibility that safety to the environment such as the human body or the ecosystem is insufficient.

  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.

  The present invention can be used as a rust-preventing oil composition and exhibits good performance particularly for metal parts subjected to heat treatment.

Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
"Examples 1-8 and Comparative Examples 1-7"
Various rust preventive oil compositions according to the present invention having the compositions shown in Examples 1 to 8 in Table 1 and rust preventive oil compositions shown in Comparative Examples 1 to 7 were prepared. The components used for the preparation of each composition are as follows.

(A) Base oil A1: Mineral oil (kinematic viscosity at 40 ° C. is 2 mm ² / s)
A2: Mineral oil (kinematic viscosity at 40 ° C. is 22 mm ² / s)
A3: Hard alkylbenzene (kinematic viscosity at 40 ° C. is 22 mm ² / s)

(B) Rust prevention additive B1: Alcohol derivative of alkylamine represented by the following formula (2).
B2: Alkylamine alcohol derivative represented by the following formula (3).
B3: Alcohol derivative of alkylamine represented by the following formula (4).
B4: Alcohol derivative of alkylamine represented by the following formula (5).
B5: Alkylamine alcohol derivative represented by the following formula (6).
B6: Alcohol derivative of alkylamine represented by the following formula (7).

(C) Other components C1: di-tert-butyl-p-cresol C2: benzotriazole C3: sorbitan monooleate C4: organic acid amine salt C5: calcium salt of alkylbenzene sulfonic acid C6: calcium salt of oxidized wax

Next, the following performance evaluation test was done about the composition of each Example 1-8 and Comparative Examples 1-7 which were prepared, respectively. The results are shown in Table 1 and Table 1 continuation.
[Rust prevention test (salt spray)] Evaluation was made using the time until rust was generated in the neutral salt spray test specified in JIS K2246 "Rust prevention oil". However, evaluation was performed every hour.
[Heat treatment test] Heat treatment was performed under the conditions shown below, and the evaluation was made by observing the appearance of the part. One point was “severe stain”, two points were “clear stain”, and “slightly stain” was 3 A score of 4 points was given to “almost deemed”.

(Heat treatment conditions)
1) Heating at 500 ° C for 1 hour in a nitrogen atmosphere 2) Heating at 880 ° C for 30 minutes 3) Quenching treatment (oil temperature 90 ° C, quenching time in quenching oil (dynamic viscosity at 40 ° C is 43 mm ² / s) (10 minutes)

(Storage stability)
80 g of sample oil is weighed in a 100 ml glass bottle and left standing for 1 month at room temperature with the stopper. Then, the thing which does not produce cloudiness and precipitation was set as the pass, and the thing which cloudy and precipitation was set as the rejection.

Claims (2)

(A) a mineral oil and / or at least one base oil selected from among synthetic oil is 70 mass% or more based on the total amount of the composition, (B) the composition of the alcohol derivative of an amine of the formula 1 the total amount A rust-preventing oil composition containing 0.5 to 25% by mass and having a kinematic viscosity at 40 ° C. of 1 to 100 mm ² / s.

(In the formula (1), R ¹ is 1,1-dimethylhexyl group, 1,1-dimethyloctyl group, 1,1-dimethylnonyl group, 1,1-dimethyldecyl group, 1,1-dimethylundecyl group. 1,1-dimethyldodecyl group, 1,1-dimethyltridecyl group, 1,1-dimethyltetradecyl group, 1,1-dimethylpentadecyl group, 1,1-dimethylhexadecyl group, 1,1-dimethyl One of a heptadecyl group, a 1,1-dimethyloctadecyl group, a 1,1-dimethylnonadecyl group and a 1,1-dimethyleicosyl group, R ² and R ³ may be the same or different; And a hydrocarbon group having 1 to 12 carbon atoms, which may be linear or branched, saturated or unsaturated.)   The rust preventive oil composition according to claim 1, wherein the total content of metal elements is less than 0.1% by mass based on the total amount of the composition.