JP2014047330A - Cleaning oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning oil composition for machine interior, which has the effect of easily peeling off metal powder adhering to the inside of a machine, and making it easy to catch even fine metal powder in a filter.SOLUTION: A cleaning oil composition contains at least one base oil selected from mineral oil and synthetic oil, and an azole compound of 0.1-50 mass% based on the total amount of the composition.

Description

  The present invention relates to a cleaning oil composition, and more particularly to a cleaning oil composition suitable for cleaning metal powder, sludge and the like inside a machine and piping, and more specifically, a rolling mill, a press device, a machine tool, The present invention relates to a cleaning oil composition suitable for cleaning the inside of hydraulic equipment, a compressor, a heat medium device, a bearing, a gear box, a heat treatment furnace, an engine, and the like.

  Many machines are manufactured through various processes. Some of the processes include cutting, shaving, and bending metal, which generates and attaches metal wear powder. When the machine is used with the metal powder remaining, the metal powder is taken into, for example, a lubricating oil used inside the machine. When the metal powder moves to the operating part of the machine, problems such as biting occur, and metal components adhere to the product manufactured by the machine, causing damage or the like.

  For this reason, the parts constituting the machine are often washed after being manufactured, and the metal powder and the like are often removed. However, when these parts are incorporated into the entire machine, there are processes such as screwing and welding, and metal powder is generated even in those processes. In addition, even if the amount of metal powder generated by assembling each part is small, in the case of a machine consisting of many parts, if the metal powder from each part is transported by oil etc. and concentrated in one place The amount is sufficient to cause defects.

  Therefore, when such a malfunction is expected, washing with a lubricant similar to the lubricating oil to be supplied is often performed (so-called flushing, co-washing, etc.) before supplying the finished machine with lubricating oil. However, it is difficult to completely remove the metal powder stuck to the inside of the pipe.

  On the other hand, mixing of metal powder becomes a problem even in a working machine. For example, the friction between the metals is constantly generated in the movable part inside the machine, so that the metal is worn and mixed with metal powder. This is clear even in familiar examples such as automobile engine oil. Further, when the machine is used for metal processing, the amount of wear powder generated from the metal to be processed is very large, and the machine operation is hindered unless these are processed efficiently.

  Therefore, in many cases, measures are taken such as installing a filter in the path through which the lubricating oil flows to capture the metal powder. However, this method has no effect on fine metal powder that is not trapped by the filter, especially dissolved in oil, and results in the deposition of fine metal powder in the oil. Since the fine wear powder has a large surface area, it causes not only a malfunction of the machine but also blackening of the lubricating oil, or it reacts with additives in the lubricating oil and causes dirt.

  As described above, there is a need for a method for cleaning and removing harmful metal powder before and after the machine is operated.

Japanese Patent Laid-Open No. 3-68691 Japanese Patent Laid-Open No. 3-68692 JP 2000-265188 A

  The present invention has been made from the above viewpoint, and provides a cleaning oil composition for machine interior that has an effect of easily peeling off metal powder adhering to the inside of a machine and facilitating capture of even fine metal powder on a filter. It is for the purpose.

  In order to solve the above problems, the present invention provides a cleaning oil containing at least one base oil selected from mineral oil and synthetic oil, and 0.1 to 50% by mass of an azole compound based on the total amount of the composition. A composition is provided.

  When the cleaning oil composition of the present invention contains less than 30% by mass of alcohol and / or ester as a base oil based on the total amount of the composition, the content of the azole compound is 0.1 to 10% by mass based on the total amount of the composition. It is preferable.

  When the cleaning oil composition of the present invention contains 30% by mass or more of alcohol and / or ester as a base oil based on the total amount of the composition, the content of the azole compound is 10 to 50% by mass based on the total amount of the composition. It is preferable.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to peel off the metal powder adhering to the inside of a machine easily, and it becomes possible to provide the washing | cleaning oil composition for machine insides which is excellent in the capture property of a filter also with a fine metal powder.

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

  The cleaning oil composition according to the embodiment of the present invention contains at least one base oil selected from mineral oil and synthetic oil, and 0.1 to 50% by mass of an azole compound based on the total amount of the composition.

  In the present embodiment, at least one selected from mineral oil and synthetic oil is used as the base oil of the cleaning oil composition.

  As mineral oils, for example, lubricating oil fractions obtained by subjecting crude oil to atmospheric distillation and vacuum distillation can be used for solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing Mineral oils such as paraffinic mineral oil and naphthenic mineral oil, which are refined by appropriately combining purification treatments such as clay treatment, can be used. In particular, it is preferable to use paraffinic mineral oil and naphthenic mineral oil having a polycyclic aromatic hydrocarbon (PCA) content of less than 3% by mass as the DMSO extract.

When using mineral oil as the base oil, it is usually advantageous to use mineral oil with a high aromatic content to dissolve the attached metal powder, but there is a risk that the metal powder particles after dissolution will become excessively fine. is there. Therefore, especially when using a mineral oil having a kinematic viscosity at 40 ° C. of 6 mm ² / s or less, the aromatic content in the mineral oil is preferably 3% by volume or less, more preferably 2% by volume or less. Most preferably, it is 1% by volume or less. The naphthene content of the mineral oil is preferably 30% by volume or more, more preferably 35% by volume or more, and most preferably 40% by volume or more.

  Synthetic oils include, for example, alcohols, esters, polyoxyalkylene glycols, polyphenyl ethers, poly α-olefins (polybutenes, 1-octene oligomers, 1-decene oligomers, etc.), polybutenes, polyisobutylenes, alkylbenzenes, alkylnaphthalenes, and the like. Can be used.

  Alcohols are monohydric alcohols, polyhydric alcohols, saturated or unsaturated, mixtures thereof, linear or branched, and mixtures thereof. Also good. A monohydric alcohol having 1 to 24 carbon atoms is preferable, a monohydric alcohol having 1 to 22 carbon atoms is more preferable, and a monohydric alcohol having 8 to 20 carbon atoms is most preferable because higher detergency is obtained. is there. Of these, branched aliphatic alcohols are preferred from the viewpoint of detergency.

  Specific examples of the monohydric alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched Hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched Decanol, straight-chain or branched Ikosanoru, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as straight-chain or branched tetracosanol, and mixtures thereof.

  Among these, branched octanols such as 2-ethylhexyl alcohol, linear and branched dodecanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, and unsaturated octane. Decel alcohol (oleyl alcohol) is preferred, 2-ethylhexyl alcohol, linear, branched dodecanol, octadecanol, and unsaturated octadecel alcohol (oleyl alcohol) are more preferred, branched dodecanol, tridecanol, tetra Most preferred are decanol, pentadecanol, and mixtures thereof.

  As the polyhydric alcohol, usually 2 to 10 valent, preferably 2 to 6 valent alcohols are used. Specific examples of the divalent to 10-valent polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 3 of propylene glycol). 15-mer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1, Dihydric alcohols such as 3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2 ~ Octamer, eg diglycerin, trig Serine, tetraglycerin, etc.), trimethylol alkanes (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and their 2-to 8-mer, pentaerythritol and their 2-to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof And the like.

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

  As the esters, fatty acid esters and phosphate ester compounds are preferred.

  As fatty acid ester, ester of said monohydric alcohol and fatty acid is preferable. The carbon number of the monohydric alcohol constituting the fatty acid ester is preferably 1 or more and 12 or less, more preferably 1 or more and 10 or less, and most preferably 1 or more and 8 or less. The monohydric alcohol may be linear or branched, and may be saturated or unsaturated, or a mixture thereof, but a linear saturated monohydric alcohol is preferred.

  Examples of the fatty acid constituting the fatty acid ester include linear or branched fatty acids having 6 to 24 carbon atoms, and may be a saturated fatty acid, an unsaturated fatty acid, or a mixture thereof.

  Saturated fatty acids include linear or branched hexanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched Dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched octadecanoic acid, linear or branched hydroxy Octadecanoic acid, linear or branched nonadecanoic acid, linear or branched eicosanoic acid, linear or branched heneicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid Etc.

  Examples of unsaturated fatty acids include linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, linear or branched Undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or branched hexadecenoic acid, linear or branched octadecene Acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecenoic acid, linear or branched eicosenoic acid, linear or branched heneicosenoic acid, linear or branched docosenoic acid, linear or branched tricosene Examples include acid, linear or branched tetracosenoic acid, and the like. Of these, saturated fatty acids having 8 to 20 carbon atoms, unsaturated fatty acids having 8 to 20 carbon atoms, and mixtures thereof are particularly preferable.

  As the fatty acid, branched octanoic acid, 2-ethylhexylic acid, linear dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, branched octadecenoic acid (oleic acid) are preferable, and 2-ethylhexyl acid, linear dodecanoic acid, octadecane Acid and branched octadecenoic acid (oleic acid) are more preferable.

  The fatty acid constituting the fatty acid ester is preferably a fatty acid having 6 to 24 carbon atoms, more preferably a fatty acid having 7 to 20 carbon atoms, and most preferably 8 to 18 carbon atoms from the viewpoint of obtaining higher detergency. Of fatty acids.

［一般式（１）中、Ｒ^１、Ｒ^２およびＲ^３は個別に水素または炭素数１〜２４の炭化水素基を示し、Ｒ^１、Ｒ^２またはＲ^３の少なくとも１つは炭素数１〜２４の炭化水素基である。］

［一般式（２）中、Ｒ^４、Ｒ^５およびＲ^６は個別に水素または炭素数１〜２４の炭化水素基を示し、Ｒ^４、Ｒ^５またはＲ^６の少なくとも１つは炭素数１〜２４の炭化水素基である。］ The phosphoric acid ester-based compounds mentioned here include a phosphoric acid ester represented by the following general formula (1) and its amine salt, a phosphorous acid ester represented by the following general formula (2) and its amine salt. included.

[In General Formula (1), R ¹ , R ² and R ³ individually represent hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, and at least one of R ¹ , R ² or R ³ represents ¹ to C carbon atoms. 24 hydrocarbon groups. ]

[In General Formula (2), R ⁴ , R ⁵ and R ⁶ individually represent hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, and at least one of R ⁴ , R ⁵ or R ⁶ has 1 to 1 carbon atoms. 24 hydrocarbon groups. ]

The amine salt of a phosphoric acid ester represented by the general formula (1), any one of R ¹ to R ³ is a hydrocarbon group, the remaining two are hydrogen monoesters or R ¹ to R ³ It means a diester in which any two are hydrocarbon groups and the remaining one is hydrogen, that is, an amine salt of acid phosphate (acidic phosphate ester). Similarly, a sub-formula represented by the general formula (2) The amine salt of phosphate ester is a monoester in which any one of R ^{4 to} R ⁶ is a hydrocarbon group and the remaining two are hydrogen, or any two of R ^{4 to} R ⁶ are hydrocarbon groups. , Means the diester wherein the remaining one is hydrogen, ie, the amine salt of hydrogen phosphite (hydrogen phosphite).

In the general formulas (1) and (2), the hydrocarbon group includes a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 3 to 24 carbon atoms, Examples thereof include a cycloalkyl group having 5 to 13 carbon atoms or an alkylcycloalkyl group, an aryl group having 6 to 18 carbon atoms, a linear or branched alkylaryl group, an arylalkyl group having 7 to 19 carbon atoms, and the like. As the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, linear or branched pentyl group, linear or branched Hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group Group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group Linear or branched heicosyl group, linear or branched docosyl group, linear or branched tricosyl group, Such chain or branched tetracosyl group. Examples of the alkenyl group include a propenyl group, an isopropenyl group, a linear or branched butenyl group, a butadienyl group, a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched octenyl group, Linear or branched nonenyl group, linear or branched decenyl group, linear or branched undecenyl group, linear or branched dodecenyl group, linear or branched tridecenyl group, linear or branched tetradecenyl group, linear or branched pentadecenyl group, straight Linear or branched hexadecenyl group, linear or branched heptadecenyl group, linear or branched octadecenyl group such as oleyl group, linear or branched nonadecenyl group, linear or branched icosenyl group, linear or branched henicosenyl group, linear or branched dococenyl Group, linear or branched tricoseni Group, straight or branched tetracosenyl group. As the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like are preferable. As the alkylcycloalkyl group, a methylcyclopentyl group, a dimethylcyclopentyl group (including all substituted isomers), and an ethylcyclopentyl group (all substitutions). Isomers), linear or branched propylcyclopentyl groups (including all substituted isomers), ethylmethylcyclopentyl groups (including all substituted isomers), trimethylcyclopentyl groups (including all substituted isomers), Diethylcyclopentyl group (including all substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers), linear or branched propylmethylcyclopentyl group (including all substituted isomers), linear or branched propyl Ethyl cyclopen Group (including all substituted isomers), di-linear or branched propylcyclopentyl group (including all substituted isomers), linear or branched propylethylmethylcyclopentyl group (including all substituted isomers), Methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), linear or branched propylcyclohexyl group (all substituted isomers) Isomers), ethylmethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (including all substituted isomers), ethyldimethylcyclohexyl group (Including all substituted isomers), linear or branched propylme Rucyclohexyl group (including all substituted isomers), linear or branched propylethylcyclohexyl group (including all substituted isomers), di-linear or branched propylcyclohexyl group (including all substituted isomers), Linear or branched propylethylmethylcyclohexyl group (including all substituted isomers), methylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), ethylcycloheptyl Groups (including all substituted isomers), linear or branched propylcycloheptyl groups (including all substituted isomers), ethylmethylcycloheptyl groups (including all substituted isomers), trimethylcycloheptyl groups (all ), Diethylcycloheptyl group (including all substituted isomers) , Ethyldimethylcycloheptyl group (including all substituted isomers), linear or branched propylmethylcycloheptyl group (including all substituted isomers), linear or branched propylethylcycloheptyl group (including all substituted isomers) Alkylcycloalkyl groups such as di-linear or branched propylcycloheptyl groups (including all substituted isomers), linear or branched propylethylmethylcycloheptyl groups (including all substituted isomers) preferable. In addition, as the aryl group of the general formulas (1) and (2), a phenyl group, a naphthyl group, and the like are preferable. Similarly, as the alkylaryl group, a tolyl group (including all substituted isomers), a xylyl group (all Including substituted isomers), ethylphenyl group (including all substituted isomers), linear or branched propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers) , Trimethylphenyl group (including all substituted isomers), linear or branched butylphenyl group (including all substituted isomers), linear or branched propylmethylphenyl group (including all substituted isomers), diethyl Phenyl group (including all substituted isomers), ethyldimethylphenyl group (including all substituted isomers), tetramethylphenyl group (including all substituted isomers) All substituted isomers included), linear or branched pentylphenyl group (including all substituted isomers), linear or branched hexylphenyl group (including all substituted isomers), linear or branched heptylphenyl Group (including all substituted isomers), linear or branched octylphenyl group (including all substituted isomers), linear or branched nonylphenyl group (including all substituted isomers), linear or branched decyl A phenyl group (including all substituted isomers), a linear or branched undecylphenyl group (including all substituted isomers), a linear or branched dodecylphenyl group (including all substituted isomers) and the like are preferable. As arylalkyl groups, benzyl, methylbenzyl (including all substituted isomers), dimethylbenzyl (including all substituted isomers), phenethyl, methylphenethyl (all substituted isomers) A dimethylphenethyl group (including all substituted isomers) and the like. Among the above hydrocarbon groups that R ^{1 to} R ³ or R ^{4 to} R ⁶ can take, the hydrocarbon group is a linear or branched alkyl group or alkenyl group having 4 to 18 carbon atoms, or 6 to 6 carbon atoms. It is even more preferable that the aryl group is 12 or a linear or branched alkylaryl group, and in particular, a linear or branched alkyl group having 4 to 18 carbon atoms, an oleyl group, a phenyl group, or a carbon number. Most preferred is a 7-9 linear or branched alkylaryl group.

  Specific preferred examples of the phosphoric acid ester represented by the general formula (1) are tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triunate. Decyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylate Triphosphates such as nyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate Monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid Phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid, dipentyl acid Dihexyl acid Sulfate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid hexaphosphate Examples thereof include acid phosphates (acidic phosphate esters) such as decyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate; and mixtures thereof.

  Preferred examples of the phosphite represented by the general formula (2) are tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite. Phyto, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, tritridecyl phosphite, tritetradecyl phosphite, tripentadecyl phosphite, trihexadecyl phosphite, triheptadecyl phosphite, trioctadecyl phosphite Triphosphites such as phite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, cresyl diphenyl phosphite, xylenyl diphenyl phosphite (Phosphorous acid triester); monobutyl hydrogen phosphite, monopentyl hydrogen phosphite, monohexyl hydrogen phosphite, monoheptyl hydrogen phosphite, monooctyl hydrogen phosphite, monononyl hydrogen phosphite, Monodecyl hydrogen phosphite, monoundecyl hydrogen phosphite, monododecyl hydrogen phosphite, monotridecyl hydrogen phosphite, monotetradecyl hydrogen phosphite, monopentadecyl hydrogen phosphite, monohexadecyl hydro Genphosphite, monoheptadecyl hydrogen phosphite, monooctadecyl hydrogen phosphite, monooleyl hydro Enphosphite, Dibutyl hydrogen phosphite, Dipentyl hydrogen phosphite, Dihexyl hydrogen phosphite, Diheptyl hydrogen phosphite, Dioctyl hydrogen phosphite, Dinonyl hydrogen phosphite, Didecyl hydrogen phosphite, Diundecyl hydro Genphosphite, didodecyl hydrogen phosphite, ditridecyl hydrogen phosphite, ditetradecyl hydrogen phosphite, dipentadecyl hydrogen phosphite, dihexadecyl hydrogen phosphite, diheptadecyl hydrogen phosphite, Hydrogen phosphites such as dioctadecyl hydrogen phosphite and dioleyl hydrogen phosphite Phyto (hydrogen phosphite); and mixtures thereof; and the like.

  As described above, as the phosphate ester compound, an amine salt of acid phosphate (acid phosphate ester) or an amine salt of hydrogen phosphite (hydrogen phosphite ester) can be used. In these amine salts, some or all of the acidic hydrogen remaining in acid phosphate or hydrogen phosphite is substituted with an alkyl group, alkenyl group or alkanol group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. Salts neutralized with amine compounds contained in the molecule are included. Specific examples of preferred amine compounds include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, monononylamine, monodecylamine, Monoundecylamine, monododecylamine, monotridecylamine, monotetradecylamine, monopentadecylamine, monohexadecylamine, monoheptadecylamine, monooctadecylamine, monononadecylamine, monoicosylamine, monoheny Cosylamine, monohencosylamine, monotricosylamine, monotetracosylamine, dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropy Amine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentaamine Alkylamines such as decylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, diicosylamine, dihenicosylamine, dihenicosylamine, ditricosylamine, ditetracosylamine The group may be linear or branched); monobutenylamine, monopentenylamine, monohexenylamine, monoheptenylamine, monooctenylamine, monononenylamine , Monodecenylamine, monoundecenylamine, monododecenylamine, monotridecenylamine, monotetradecenylamine, monopentadecenylamine, monohexadecenylamine, monoheptadecenylamine, monooctadecenylamine Cenylamine, monononadecenylamine, monoicocenylamine, monohenecocenylamine, monohenecocenylamine, monotricocenylamine, monotetracocenylamine, dibutenylamine, dipentenylamine, dihexenylamine, diheptenylamine , Dioctenylamine, dinonenylamine, didecenylamine, diundecenylamine, didodecenylamine, ditridecenylamine, ditetradecenylamine, dipentadecenylamine, dihexadecenylamine, diheptadecenylamine, Alkenylamines such as dioctadecenylamine, dinonadecenylamine, diicosenylamine, dihenicosenylamine, dihenicocenylamine, ditricosenylamine, ditetracosenylamine (alkenyl groups are linear or branched) Monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptanolamine, monooctanolamine, monononanolamine, monodecanolamine, monoun Decanolamine, monododecanolamine, monotridecanolamine, monotetradecanolamine, monopentadecanolamine, monohexadecanolamine, monoheptadecanolamine, monooctadecanolamine , Monononadecanolamine, monoicosanolamine, monohenicosanolamine, monohenicosanolamine, monotricosanolamine, monotetracosanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanol Propanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipentanolamine, dihexanolamine, diheptanolamine, dioctanolamine, dinonanolamine, didecanolamine, Diundecanolamine, didodecanolamine, ditridecanolamine, ditetradecanolamine, dipentadecanolamine , Dihexadecanolamine, diheptadecanolamine, dioctadecanolamine, dinonadecanolamine, diicosanolamine, dihenicosanolamine, dihenicosanolamine, ditricosanolamine, ditetracosa Examples thereof include alkanolamines such as noramine (the alkanol group may be linear or branched); and mixtures thereof; among these, 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, An alkylamine containing an alkyl group having 1 to 8 carbon atoms in the molecule is preferable.

  When an amine salt is used in the cleaning oil composition according to the present embodiment, the amine salt is acid phosphate (acidic phosphate ester) or hydrogen phosphite (hydrogen phosphite), methylamine, ethylamine, propylamine. , Butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine Particularly preferred are salts with amines such as tripentylamine, trihexylamine, triheptylamine, and trioctylamine. The phosphate ester compound contained in the cleaning oil composition of the present invention includes the above-described phosphate ester, phosphite ester, acid phosphate (acid phosphate ester) and hydrogen phosphite (hydrogen phosphite ester). A mixture in an arbitrary ratio of two or more kinds of compounds selected from the group consisting of amine salts can also be used.

  Among phosphoric acid ester compounds, phosphoric acid triesters are preferable, and tricresyl phosphate is most preferable.

  Of the above alcohols and esters, branched aliphatic alcohols are preferred, specifically, branched dodecanol, branched tridecanol, branched tetradecanol, branched pentadecanol, and mixtures thereof. Most preferred.

  In the present embodiment, the content of the base oil is 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more based on the total amount of the composition. The content of the base oil is 99.9% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less, based on the total amount of the composition.

  Further, the cleaning oil composition according to this embodiment contains less than 30% by mass of alcohol and / or ester as a base oil based on the total amount of the composition, and 0.1 to 10% by mass of the azole compound based on the total amount of the composition. In this case, the base oil may be a mixed base oil of alcohol and / or ester and another base oil, or may be a base oil containing no alcohol and ester. The base oil content in this case (mixed base oil content in the case of mixed base oil) is 99.9% by mass or less, preferably 97% by mass or less, and preferably 95% by mass or less, based on the total amount of the composition. Particularly preferred.

  Further, when the cleaning oil composition according to the present embodiment contains 30% by mass or more of alcohol and / or ester as a base oil based on the total amount of the composition, and the azole compound contains 10 to 50% by mass based on the total amount of the composition, The base oil may be composed only of alcohol and / or ester, or may be a mixed base oil of alcohol and / or ester and other base oil (synthetic oil and mineral oil other than alcohol and ester). . When the base oil is composed only of alcohol and / or ester, the content of the base oil is 90% by mass or less, preferably 87% by mass or less, and most preferably 85% by mass or less in the total amount of the composition. When the base oil is a mixed base oil of alcohol and / or ester and other base oil, the total amount of the other base oil is preferably 20% by mass or less of the total amount of alcohol and ester, and 10 mass. % Or less is more preferable.

In this embodiment, the kinematic viscosity of the base oil is not particularly limited, but the kinematic viscosity of the base oil at 40 ° C. is preferably 0.8 mm ² / s or more, more preferably 1.0 mm ² / s or more, and 1.2 mm. ² / s or more is most preferable. Moreover, kinematic viscosity at 40 ° C. of the base oil is preferably not more than 50 mm ² / s, more preferably not more than 40 mm ² / s, most preferably at most 30 mm ² / s.

Moreover, the mineral oil as a base oil may be used individually by 1 type, or may be used in combination of 2 or more type. When combining two or more mineral oils, it is preferable from the viewpoint of detergency to use a mineral oil having a kinematic viscosity at 40 ° C. of 6 mm ² / s or less and a mineral oil of 20 to 100 mm ² / s in combination. In that case, the proportion of mineral oil having a kinematic viscosity at 40 ° C. of 20 to 100 mm ² / s is preferably 5% by mass or more and 30% by mass or less based on the total amount of the base oil.

  The azole compound is a compound selected from the following (a) to (f).

［一般式（４）中、Ｒ^７は炭素数１〜４のアルキル基、ａは１〜３の整数を示す。］

［一般式（５）中、Ｒ^８およびＲ^９はそれぞれ炭素数１〜４のアルキル基を示し、それらはたがいに同一でも異なっていてもよく、ｂは０〜３の整数を示す。）

［一般式（６）中、Ｒ^１０は炭素数１〜４のアルキル基を示し、Ｒ^１１はメチレン基またはエチレン基を示し、Ｒ^１２およびＲ^１２はそれぞれ水素原子または炭素数１〜１２のアルキル基を示し、それらはたがいに同一でも異なっていてもよく、ｃは０〜３の整数を示す。］ (A) Benzotriazole or derivative thereof Compound (a) is benzotriazole or a derivative thereof represented by the following formula (3). The benzotriazole derivatives include alkylbenzotriazole represented by the following general formula (4), N-alkylbenzotriazole represented by the general formula (5), and N- (alkyl) represented by the following general formula (6). Aminoalkylbenzotriazoles are included.

[In General Formula (4), R ⁷ represents an alkyl group having 1 to 4 carbon atoms, and a represents an integer of 1 to 3. ]

[In General Formula (5), R ⁸ and R ⁹ each represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and b represents an integer of 0 to 3. )

[In General Formula (6), R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, R ¹¹ represents a methylene group or an ethylene group, and R ¹² and R ¹² represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, respectively. A group, which may be the same or different, and c represents an integer of 0 to 3; ]

R ⁷ in the general formula (4) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. a represents an integer of 1 to 3, preferably 1 or 2.

R ⁸ and R ⁹ in the general formula (5) each represent an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples of R ⁸ and R ⁹ are the same as those of R ⁷ . b is an integer of 0 to 3, preferably 0 or 1.

R ¹⁰ in the general formula (6) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. A specific example of R ¹⁰ is the same as that of R ⁷ . R ¹¹ represents a methylene group or an ethylene group, and a methylene group is preferable. R ¹² and R ¹³ each represent hydrogen or an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 9 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, and various heptyls. Groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, and various dodecyl groups. c is an integer of 0 to 3, preferably 0 or 1. Of the benzotriazoles and derivatives thereof described above, benzotriazole and N-methylbenzotriazole are particularly preferable.

［一般式（８）中、Ｒ^１４は炭素数１〜４のアルキル基を示し、ｄは１〜３の整数を示す。］

［一般式（９）中、Ｒ^１５は炭素数１〜４のアルキル基を示し、Ｒ^１６は炭素数１〜２０のアルキル基を示し、ｅは０〜３の整数を示し、ｆは１〜３の整数を示す。］ (B) Benzimidazole or its derivative Compound (b) is benzimidazole or its derivative represented by the following formula (7). Benzimidazole derivatives include alkylbenzimidazoles represented by the following general formula (8) and 2- (alkylthio) -benzimidazoles represented by the general formula (9).

[In the general formula ^{(8), R 14} represents an alkyl group having 1 to 4 carbon atoms, d is an integer of 1-3. ]

[In General Formula (9), R ¹⁵ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms, e represents an integer of 0 to 3, and f represents 1 to An integer of 3 is shown. ]

R ¹⁴ in the general formula (8) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. d represents an integer of 1 to 3, preferably 1 or 2.

R ¹⁵ in the general formula (9) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples of R ¹⁵ are the same as those of R ¹⁴ . R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups Groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicosyl groups. e is an integer of 0 to 3, preferably 0 or 1. f is an integer of 1 to 3, preferably 1 or 2. Among the benzimidazoles or derivatives thereof described above, 2- (n-dodecyldithio) -benzimidazole and 2- (n-decylthio) -benzimidazole are particularly preferable.

［一般式（１１）中、Ｒ^１７は炭素数１〜４のアルキル基を示し、ｇは１〜３の整数を示す。］ (C) Benzopyrazole or its derivative Compound (c) is benzopyrazole or its derivative represented by the following formula (10). The benzopyrazole derivative includes an alkylbenzopyrazole represented by the following general formula (11).

[In General Formula (11), R ¹⁷ represents an alkyl group having 1 to 4 carbon atoms, and g represents an integer of 1 to 3. ]

R ¹⁷ in the general formula (11) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. g represents a number of 1 to 3, preferably 1 or 2. Of the benzopyrazoles and derivatives thereof described above, benzopyrazole is particularly preferable.

［一般式（１２）中、Ｒ^１８は炭素数１〜４のアルキル基を示し、Ｒ^１９は炭素数１〜２０のアルキル基を示し、ｈは０〜３の整数を示し、ｉは１〜３の整数を示す。］

［一般式（１３）中、Ｒ^２０は炭素数１〜４のアルキル基を示し、Ｒ^２１およびＲ^２２は同一でも異なっていてもよく、それぞれ炭素数１〜１２のアルキル基を示し、ｊは０〜３の整数を示す。］ (D) Benzothiazole derivative Compound (d) is a benzothiazole derivative. The benzothiazole derivatives include 2- (alkylthio) -benzothiazole represented by the following general formula (12) and 2- (N, N-dialkyldithiocarbamyl) -benzothiazole represented by the general formula (13). Is included.

[In General Formula (12), R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁹ represents an alkyl group having 1 to 20 carbon atoms, h represents an integer of 0 to 3, and i represents 1 to 1 An integer of 3 is shown. ]

[In General Formula (13), R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, R ²¹ and R ²² may be the same or different, and each represents an alkyl group having 1 to 12 carbon atoms; An integer of 0 to 3 is shown. ]

R ¹⁸ in the general formula (12) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R13 represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups Groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicosyl groups. h is an integer of 0 to 3, preferably 0 or 1. i is an integer of 1 to 3, preferably 1 or 2.

R ²⁰ in the general formula (13) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R ²¹ and R ²² each represent an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, and various heptyls. Groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, and various dodecyl groups. j is an integer of 0 to 3, preferably 0 or 1. Among the benzothiazole derivatives described above, 2- (n-dodecyldithio) -benzothiazole, 2- (n-decylthio) -benzothiazole; 2- (N, N-diethyldithiocarbamyl) -benzothiazole is particularly preferable. preferable.

［一般式（１４）中、Ｒ^２３は炭素数１〜４のアルキル基を示し、Ｒ^２４は炭素数１〜２０のアルキル基を示し、ｋは０〜３の整数を示し、ｍは１〜３の整数を示す。］ (E) Benzoxazole derivative The compound (e) is a benzoxazole derivative. The benzoxazole derivative includes 2- (alkylthio) -benzoxazole represented by the following general formula (14).

[In General Formula (14), R ²³ represents an alkyl group having 1 to 4 carbon atoms, R ²⁴ represents an alkyl group having 1 to 20 carbon atoms, k represents an integer of 0 to 3, and m represents 1 to An integer of 3 is shown. ]

R ²³ in the general formula (14) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R ²⁴ represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups Groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicosyl groups. k is an integer of 0 to 3, preferably 0 or 1. m is an integer of 1 to 3, preferably 1 or 2. Among the benzoxazole derivatives described above, 2- (n-dodecyldithio) -benzoxazole and 2- (n-decylthio) -benzoxazole are particularly preferable.

［一般式（１５）中、Ｒ^２５は炭素数１〜２０のアルキル基を示し、ｎは１〜３の整数を示す。］

［一般式（１６）中、Ｒ^２６およびＲ^２７は同一でも異なっていてもよく、それぞれ炭素数１〜１２のアルキル基を示す。］ (F) Thiadiazole derivative Compound (f) is a thiadiazole derivative. The thiadiazole derivatives include 2,5-bis (alkyldithio) -1,3,4-thiadiazole represented by the following general formula (15) and 2,5-bis (N, N-dialkylcythiocarbamyl) -1,3,4-thiadiazole is included.

[In General Formula (15), R ²⁵ represents an alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3. ]

[In General Formula (16), R ²⁶ and R ²⁷ may be the same or different and each represents an alkyl group having 1 to 12 carbon atoms. ]

R ²⁵ in the general formula (15) represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups Groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicosyl groups. n is an integer of 1 to 3, preferably 1 or 2.

R ²⁶ and R ²⁷ in the general formula (16) each represent an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, and various heptyls. Groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, and various dodecyl groups. Among the thiadiazole derivatives described above, 2,5-bis (n-dodecyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-octyldithio) -1,3,4-thiadiazole, 2,5-bis (N, N-diethyldithiocarbamyl) -1,3,4-thiadiazole is preferred.

  Among the azole compounds, specifically, benzotriazole derivatives are preferred, and benzotriazole is most preferred.

  In this embodiment, the said azole compound may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the azole compound is 0.1% by mass or more, preferably 1% by mass or more, and most preferably 3% by mass or more based on the total amount of the composition. Moreover, the said content is 50 mass% or less, Preferably it is 45 mass% or less, Most preferably, it is 40 mass% or less.

  When alcohol and / or ester is contained as a base oil in an amount of less than 30% by mass based on the total amount of the composition, the upper limit of the amount of the azole compound is 10% by mass based on the total amount of the composition, preferably 8% by mass, most preferably Is 5% by mass.

When alcohol and / or ester is contained as the base oil in an amount of 30% by mass or more based on the total amount of the composition, the lower limit of the amount of the azole compound is 10% by mass based on the total amount of the composition, preferably 13% by mass, Preferably it is 15 mass%.
If the amount of azole compound added is small, a sufficient cleaning effect will not be obtained, and if it is too much, an effect commensurate with the amount added will not be obtained, but the metal powder will become too coarse, which may cause dirt due to filter clogging and reattachment There is a case.

  Other additives that can be blended in the cleaning oil composition according to this embodiment include oily agents such as fatty acids; sulfur-based extreme pressure agents such as sulfide mineral oil and sulfide esters; phenol-based antioxidants, amine-based antioxidants, and the like. Various known additives such as a dispersant, a corrosion inhibitor, an antifoaming agent, and a surfactant can be appropriately blended. The total amount of these other additives is usually in the range of 0.01 to 15% by weight based on the total amount of the composition.

  When cleaning is performed using the cleaning oil composition according to this embodiment, the cleaning oil composition itself according to this embodiment may be cleaned, or the cleaning oil composition according to this embodiment may be washed with other base oils or It can also be used diluted with a lubricating oil or oil. In particular, when used for cleaning a machine in use, it is desirable to dilute with a lubricating oil or oil used in the machine. In that case, the blending amount of the cleaning oil composition to be used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more based on the total amount of the lubricating oil or oil used in the machine, 0.1% The mass% or more is most preferable. Moreover, 10 mass% or less is preferable, 5 mass% or less is more preferable, and 1 mass% or less is the most preferable.

“Kinematic viscosity” means a kinematic viscosity measured according to JIS K2283.
“Aromatic content” is measured in accordance with the Japan Petroleum Institute Method JPI-5S-49- “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method”. It means the volume percentage (volume%) of the aromatic content measured.
“Naphthene content” means the volume percentage (volume%) of naphthene content measured according to ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”.

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

[Examples 1-60, Comparative Examples 1-5]
In Examples 1 to 60 and Comparative Examples 1 to 5, sample oils as cleaning oil compositions having the compositions shown in Tables 1 to 7 were prepared using the base oils and additives shown below, respectively.
In each sample oil preparation, each additive was blended into the base oil and then gently stirred for 1 hour at 80 ° C. After that, if precipitation or turbidity occurred in the prepared sample oil, the sample oil was stirred vigorously. After making uniform, it used for evaluation.
[Base oil]
A1: Mineral oil (kinematic viscosity at 40 ° C. 0.5 mm ² / s aromatic content 0.4 vol% naphthene content 49 vol%)
A2: Mineral oil (kinematic viscosity at 40 ° C. 0.9 mm ² / s aromatic content 0.8 volume% naphthene content 51 volume%)
A3: Mineral oil (kinematic viscosity at 40 ° C. 2.8 mm ² / s aromatic content 0.4 vol% naphthene content 45 vol%)
A4: Mineral oil (kinematic viscosity at 40 ° C. 2.6 mm ² / s aromatic content 4.4 vol% naphthene content 21 vol%)
A5: Mineral oil (kinematic viscosity at 40 ° C. 2.7 mm ² / s aromatic content 4.1 vol% naphthene content 55 vol%)
A6: Mineral oil (kinematic viscosity at 40 ° C. 2.6 mm ² / s aromatic content 0.1 vol% naphthene content 19 vol%)
A7: Mineral oil (kinematic viscosity at 40 ° C. 5.5 mm ² / s aromatic content 0.3 vol% naphthene content 48 vol%)
A8: Mineral oil (kinematic viscosity at 40 ° C. 28 mm ² / s)
A9: Mineral oil (kinematic viscosity at 40 ° C. 46 mm ² / s)
A10: Mineral oil (kinematic viscosity at 40 ° C. 54 mm ² / s)
A11: Isoparaffin (kinematic viscosity at 40 ° C. 23 mm ² / s)
A12: Polyalphaolefin (kinematic viscosity at 40 ° C. 17 mm ² / s)
A13: oleyl alcohol A14: branched aliphatic alcohol mixture of 12 to 15 carbon atoms A15: lauryl alcohol A16: methyl laurate A17: butyl stearate A18: tricresyl phosphate A19: dilauryl hydrogen phosphite A20: Dihexylamine salt of dilauryl hydrogen phosphite
[Azole compounds]
B1: Benzotriazole B2: Alkylbenzotriazole (a compound represented by the general formula (4), wherein R ⁷ is a methyl group and a is 1)
B3: N-alkylbenzotriazole (a compound represented by the general formula (5), wherein R ⁸ is a methyl group, R ⁹ is an ethyl group, and b is 1)
B4: N- (alkyl) aminoalkylbenzotriazole (represented by the general formula (6), R ¹⁰ is a methyl group, R ¹¹ is a methylene group, R ¹² is an ethyl group, R ¹³ is an ethyl group, and c is 1 Compound)
B5: Benzimidazole B6: Alkylbenzimidazole (compound represented by the general formula (8), R ¹⁴ is an ethyl group, and d is 2)
B7: 2- (alkylthio) -benzimidazole (compound represented by the general formula (9), wherein R ¹⁵ is an ethyl group, R ¹⁶ is a dodecyl group, e is 1, and f is 2)
B8: Benzopyrazole B9: Alkylbenzopyrazole (compound represented by the general formula (11), wherein R ¹⁷ is a methyl group and g is 2)
B10: 2- (alkylthio) -benzothiazole (a compound represented by the general formula (12), wherein R ¹⁸ is a methyl group, R ¹⁹ is a dodecyl group, h is 1, and i is 2)
B11: 2- (N, N-dialkyldithiocarbamyl) -benzothiazole (represented by the general formula (13), R ²⁰ is an ethyl group, R ²¹ is an ethyl group, R ²² is an ethyl group, and j is 1 Compound)
B12: 2- (alkylthio) -benzoxazole (compound represented by the general formula (14), R ²³ is an ethyl group, R ²⁴ is a decyl group, k is 1, and m is 1)
B13: 2,5-bis (alkyldithio) -1,3,4-thiadiazole (a compound represented by the general formula (15), wherein R ²⁵ is a dodecyl group and n is 2)
B14: 2,5-bis (N, N-dialkylcythiocarbamyl) -1,3,4-thiadiazole (a compound represented by the general formula (16), wherein R ²⁶ is an ethyl group and R ²⁷ is an ethyl group) )
[Other additives]
D1: Oleic acid D2: Sulfurized ester (sulfurized oil and fat) (sulfur content 24 mass%)
D3: 2,6-ditertiary butyl-p-cresol (DBPC)

  Next, the following evaluation tests were performed on the cleaning oil compositions of Examples 1 to 60 and Comparative Examples 1 to 5.

(Cleanability test 1)
This test is an evaluation method assuming that the machine is cleaned before operation.
General-purpose water-soluble cutting classified as A1 by JIS K2241 “Cutting oil” and metal powder (average particle size: 3.6 μm, Fe 98% or more) collected from the inside of machine tools that mainly drill holes in steel. A 60 mm (width) x 80 mm (height) x 1 mm (thickness) SPCC steel plate is immersed in a mixture of oil stock solution at a mass ratio of 1: 1 and pulled up for 5 minutes, and then horizontally with the evaluation surface facing up. The test piece was kept for 24 hours at 80 ° C. and dried.
Next, the cleaning property test was done with the sample oil which adjusted the prepared test piece to 40 degreeC. Cleaning was performed for 60 seconds using a reciprocating device used in the fingerprint removability test method of JIS K2246 “rust prevention oil”.
After washing, the test piece was taken out and the washing performance was evaluated by visually observing the state of adhesion of the metal powder. The evaluation method was based on the “rust generation measurement method” defined in JIS K2246 “rust prevention oil”, and the test piece surface was divided into 100 squares and evaluated according to the following criteria. The obtained results are shown in Tables 1-7. The evaluation was carried out 3 times and the results of 3 times were written together.
A: Metal powder remaining area ratio 0%
B: Metal powder remaining area ratio 1 to 10%
C: Metal powder remaining area ratio 11-25%
D: Metal powder remaining area ratio 26% or more

(Detergency test 2)
This test is an evaluation method assuming machine cleaning after operation.
Aluminum wear powder (average particle diameter: 0.16 μm, AL 94% or more) was collected from a filter portion provided in an aluminum cold rolling mill. The wear powder was dispersed in kerosene so that the aluminum concentration was about 100 ppm. 0.5% by mass of sample oil was added to this dispersion, vigorously stirred for 60 seconds, and then allowed to stand at room temperature for 24 hours. Thereafter, the solution was filtered under reduced pressure using a 1 μm filter, and the aluminum concentration (ppm) in the filtrate was measured. The obtained results are shown in Tables 1-7.

(Cleanability test 3)
This test is an evaluation method assuming machine cleaning after operation.
Oils from processing machines that were stamped and drawn with pure copper materials were collected. In order to remove large metal powder and dust, filtration was performed in advance with a filter having a diameter of 5 μm. The copper concentration in the oil thus obtained was 68 ppm. In addition, since a particle size is less than the minimum of a measurement, it cannot measure, and it can be estimated that the copper powder does not have a particle size but is dissolved in oil.
1 mass% of sample oil was added to this oil agent, and after vigorously stirring for 60 seconds, it was allowed to stand at room temperature for 24 hours. After standing, the solution was filtered under reduced pressure using a 1 μm-diameter filter, and the copper concentration (ppm) in the filtrate was measured. The obtained results are shown in Tables 1-7.

Claims (3)

  A cleaning oil composition comprising at least one base oil selected from mineral oil and synthetic oil, and 0.1 to 50% by mass of an azole compound based on the total amount of the composition.   The alcohol and / or ester as the base oil is contained in an amount of less than 30% by mass based on the total amount of the composition, and the content of the azole compound is 0.1 to 10% by mass based on the total amount of the composition. Cleaning oil composition.   The cleaning oil according to claim 1, wherein the base oil contains 30% by mass or more of alcohol and / or ester based on the total amount of the composition, and the content of the azole compound is 10 to 50% by mass based on the total amount of the composition. Composition.