WO2013140651A1 - さび止め油組成物 - Google Patents
さび止め油組成物 Download PDFInfo
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- WO2013140651A1 WO2013140651A1 PCT/JP2012/077883 JP2012077883W WO2013140651A1 WO 2013140651 A1 WO2013140651 A1 WO 2013140651A1 JP 2012077883 W JP2012077883 W JP 2012077883W WO 2013140651 A1 WO2013140651 A1 WO 2013140651A1
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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Definitions
- the present invention relates to a rust preventive oil composition.
- Metal members mainly composed of iron are often manufactured through processing such as cutting and pressing. Further, rust-preventing oil is applied for the purpose of preventing discoloration called rust or stain during production or when shipping as a product.
- the main purpose of the use of rust preventive oil is to prevent oxidation of the metal, that is, rust (rust) by forming a film on the metal surface and blocking oxygen.
- rust prevention oil is often used after washing and removing chloride with NP-0 fingerprint removal type rust prevention oil stipulated in JIS K2246.
- water displacement refers to the ability of an additive in an oil agent to enter between water and metal and remove water from the metal surface.
- NP-3-1 classified by JIS K 2246.
- the oil agent corresponding to NP-3-2 also has water displaceability, but this relates to rust preventive properties when water is mixed in rust preventive oil and defines the ability to remove water from the metal surface. It is not a thing (refer nonpatent literature 1).
- water-removability the ability to remove water from the metal surface is referred to as “water-removability”, and is distinguished from water-replaceability prescribed by JIS.
- the present invention has been made in view of such a situation, and an object thereof is to remove moisture attached to various metal-worked parts such as steel plates, bearings, steel balls, guide rails, and metal parts.
- An object of the present invention is to provide a rust preventive oil composition having performance and capable of obtaining sufficient rust preventive properties.
- the rust preventive oil composition of the present invention is A first mineral oil that is a mineral oil having a kinematic viscosity at 40 ° C. of 6 mm 2 / s or less; A second mineral oil that is a mineral oil having a kinematic viscosity at 40 ° C. of 250 mm 2 / s or more; Fatty acid amine salts, Ester and One or more rust inhibitors selected from the group consisting of sarcosine type compounds, nonionic surfactants, sulfonates, amines, carboxylic acids, fatty acid amine salts, carboxylates, paraffin waxes, oxidized wax salts and boron compounds; , Containing.
- the rust preventive oil composition of the present invention preferably further contains a third mineral oil that is a mineral oil having a kinematic viscosity at 40 ° C. of 10 mm 2 / s to 120 mm 2 / s.
- the aromatic content of the first mineral oil is preferably 3% by mass or less based on the total amount of the first mineral oil.
- the rust prevention oil composition of the present invention is the time for maintaining the rust generation degree A (rust generation degree 0%) in the neutral salt spray test specified in JIS K 2246 “rust prevention oil”. It is preferable to satisfy the requirement that is at least 16 hours.
- a rust-preventing oil composition capable of obtaining excellent water removal performance and further capable of suppressing the occurrence of rust over a long period of time.
- Rust prevention oil composition according to an embodiment of the present invention, (A-1) Mineral oil (first mineral oil) having a kinematic viscosity at 40 ° C. of 6 mm 2 / s or less, (A-2) Mineral oil (second mineral oil) having a kinematic viscosity at 40 ° C. of 250 mm 2 / s or more, (B) a fatty acid amine salt; (C) an ester; (D) one or more rust selected from the group consisting of sarcosine type compounds, nonionic surfactants, sulfonates, amines, carboxylic acids, fatty acid amine salts, carboxylates, paraffin waxes, oxidized wax salts and boron compounds.
- a stopper Containing.
- A-1) Mineral oil having a kinematic viscosity at 40 ° C. of 6.0 mm 2 / s or less (hereinafter also referred to as low viscosity base oil) and (A-2) Mineral oil having a kinematic viscosity at 40 ° C. of 250 mm 2 / s or more ( Hereinafter, also referred to as a high viscosity base oil) is a constituent of the base oil.
- component (A) or mineral oil base oil is referred to as component (A) or mineral oil base oil.
- the kinematic viscosity at 40 ° C. of the low-viscosity base oil is 6.0 mm 2 / s or less, preferably 5.0 mm 2 / s or less, more preferably 4.0 mm 2 / s or less, more preferably 3.0 mm 2 / s. It is as follows. When the kinematic viscosity exceeds the upper limit, it is difficult to obtain sufficient rust prevention properties.
- the kinematic viscosity at 40 ° C. of the low-viscosity base oil is preferably 0.5 mm 2 / s or more, more preferably 1.0 mm 2 / s or more, and further preferably 1.5 mm 2 / s or more. When the kinematic viscosity is less than the lower limit, the handleability tends to deteriorate.
- the kinematic viscosity at 40 ° C. of the high-viscosity base oil is 250 mm 2 / s or more, preferably 300 mm 2 / s or more, more preferably 400 mm 2 / s or more, and further preferably 450 mm 2 / s or more.
- the kinematic viscosity at 40 ° C. of the high-viscosity base oil is preferably 700 mm 2 / s or less, more preferably 650 mm 2 / s or less, and further preferably 600 mm 2 / s or less.
- the said kinematic viscosity exceeds the said upper limit, it exists in the tendency for stability of a rust prevention oil composition to become inadequate.
- a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking,
- the paraffinic or naphthenic mineral oil obtained by appropriately combining one or more kinds of purification means such as solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment, the above 40 Examples thereof include those having a kinematic viscosity at ° C.
- the aromatic content contained in the low-viscosity base oil is preferably 3% by mass or less.
- the aromatic content in the low-viscosity base oil is 3% by mass or less, the work environment such as reduction in odor and skin irritation can be improved, and further, when a large amount of water is mixed in the rust prevention oil composition The water separation performance can be improved, and the effect of extending the life of the oil can be obtained even when a large amount of water is removed.
- the aromatic content means a value measured in accordance with the fluorescent indicator adsorption method of JIS K 2536-1996 “Petroleum product-component test method”.
- the content of the low-viscosity base oil is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, based on the total amount of the composition. Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less.
- the content of the low-viscosity base oil is less than the above lower limit value, the rust prevention property tends to be insufficient, and when the content exceeds the above upper limit value, the rust prevention property tends to be insufficient.
- the content of the high-viscosity base oil is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably 35% by mass or less, based on the total amount of the composition. Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less.
- the content of the high-viscosity base oil is less than the above lower limit value, rust prevention properties tend to be insufficient, and when the content exceeds the upper limit value, water removability tends to be insufficient.
- the ratio of the high viscosity base oil to the total of the low viscosity base oil and the high viscosity base oil is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably It is 45 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 25 mass% or less.
- the ratio of the high-viscosity base oil is less than the above lower limit value, the rust prevention property tends to be lowered, and when it exceeds the upper limit value, the water removability tends to be lowered.
- the component (A) includes (A-3) a mineral oil having a kinematic viscosity at 40 ° C. of 10 mm 2 / s to 120 mm 2 / s (hereinafter, medium viscosity mineral oil) (Also called).
- the kinematic viscosity at 40 ° C. of the medium viscosity base oil is 10 mm 2 / s or more, preferably 15 mm 2 / s or more, more preferably 18 mm 2 / s or more, further preferably 20 mm 2 / s or more, and 120 mm 2. / S or less, preferably 100 mm 2 / s or less, more preferably 80 mm 2 / s or less, and even more preferably 70 mm 2 / s or less.
- the effect of improving the rust resistance due to the use of a medium viscosity base oil tends to be insufficient, and if it exceeds the above upper limit value, water removal due to the use of a medium viscosity base oil There is a tendency that the effect of improving the property is insufficient.
- the content of the medium viscosity base oil is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass based on the total amount of the composition. % Or less, more preferably 20% by mass or less.
- the content is within the above range, the effect of improving rust prevention and the effect of improving water removability due to the addition of a medium viscosity base oil can be effectively obtained.
- the ratio of the high viscosity base oil in the total of the low viscosity base oil, the medium viscosity base oil and the high viscosity base oil is preferably 1% by mass or more, more preferably 2% by mass or more. More preferably, it is 3% by mass or more, preferably 45% by mass or less, more preferably 35% by mass or less, and further preferably 25% by mass or less.
- the ratio of the high-viscosity base oil is less than the above lower limit value, the rust prevention property tends to be lowered, and when it exceeds the upper limit value, the water removability tends to be lowered.
- the content of the component (A) in this embodiment is preferably 60 based on the total amount of the composition. It is at least 70% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass, preferably at most 95% by mass, more preferably at most 90% by mass, even more preferably at most 85% by mass.
- the fatty acid constituting the (B) component fatty acid amine salt may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Also, the carbon number is not particularly limited, but those having 8 to 18 carbon atoms are preferable. Examples of the amine include monoamine, polyamine, alkanolamine and the like.
- the monoamine include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylaminetriethylamine, monopropylamine (including all isomers), dipropylamine (including all isomers), trimethylamine, Propylamine (including all isomers), monobutylamine (including all isomers), dibutylamine (including all isomers), tributylamine (including all isomers), monopentylamine (all including all isomers) Including isomers), dipentylamine (including all isomers), tripentylamine (including all isomers), monohexylamine (including all isomers), dihexylamine (including all isomers) ), Monoheptylamine (including all isomers), diheptylamine (all isomers) ), Monooctylamine (including all isomers), dioctylamine (including all isomers), monononylamine (including all isomers), mono
- Monoamines having alkyl and cycloalkyl groups (methylcyclopentyl) amine (including all substituted isomers), bis (methylcyclopentyl) amine (including all substituted isomers), (dimethylcyclopentyl) amine (all substituted isomers) Isomers), bis (dimethylcyclopentyl) amine (including all substituted isomers), (ethylcyclopentyl) amine (including all substituted isomers), bis (ethylcyclopentyl) amine (including all substituted isomers) Including), ( Methylethylcyclopentyl) amine (including all substituted isomers), bis (methylethylcyclopentyl) amine (including all substituted isomers), (diethylcyclopentyl) amine (including all substituted isomers), (methylcyclohexyl) ) Amine (including all substituted isomers), bis (methylcyclohexyl) amine (
- the monoamine also includes monoamines derived from fats and oils such as beef tallow amine.
- Specific examples of the polyamine include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine.
- alkanolamine examples include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, Tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine (including all isomers), dibutanolamine (including all isomers), tributanolamine (all Isomers), monopentanolamine (including all isomers), dipentanolamine (including all isomers), tripentanolamine (including all isomers), monohexanolamine (all Isomers), Hexanolamine (including all isomers), monoheptanolamine (including all isomers), diheptanolamine (including all isomers), monooctanolamine (including all isomers), monono Nanolamine (including all all
- monoamines are preferable because they have little influence on the refrigeration system.
- alkylamines monoamines having alkyl groups and alkenyl groups, monoamines having alkyl groups and cycloalkyl groups, cycloalkylamines, and Alkylcycloalkylamine is more preferred.
- an amine having a total carbon number of 3 or more in the amine molecule is preferable, and an amine having a total carbon number of 5 or more is more preferable.
- the content of the fatty acid amine salt is not particularly limited, but is preferably 2% by mass or more, more preferably 2.5% by mass or more, further preferably 3% by mass or more, and preferably 10% by mass based on the total amount of the composition. % Or less, more preferably 9% by mass or less, and still more preferably 8% by mass or less.
- the content of the fatty acid amine salt is less than the above lower limit value, the water removability tends to decrease, and when the content exceeds the above upper limit value, the rust prevention property tends to decrease.
- (C) component ester includes (C-1) partial ester of polyhydric alcohol, (C-2) esterified oxidized wax, (C-3) esterified lanolin fatty acid, (C-4) alkyl or alkenyl And succinic acid esters.
- (C-1) A 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. Any number 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. Polyhydric alcohols are preferably used.
- 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.
- the carboxylic acid constituting the partial ester any one can be used, and the carboxylic acid preferably has 2 to 30 carbon atoms, more preferably 6 to 24 carbon atoms, still more preferably 10 to 22 carbon atoms.
- the carboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, and may be a linear carboxylic acid or a branched carboxylic acid.
- fatty acids examples include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Saturated fatty acids such as hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triaconta
- Hydroxycarboxylic acid may be used as the carboxylic acid constituting the partial ester.
- the hydroxycarboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, but a saturated carboxylic acid is preferred from the viewpoint of stability.
- the hydroxycarboxylic acid may be a straight chain carboxylic acid or a branched carboxylic acid, but a straight chain carboxylic acid or a branched chain having 1 or 2 carbon atoms, more preferably 1 carbon atom, that is, a methyl group having 1 to 3 carbon atoms.
- a branched carboxylic acid having 1, 2 or more, particularly preferably 1 is preferable.
- the number of carbon atoms of the hydroxycarboxylic acid is preferably 2 to 40, more preferably 6 to 30, and still more preferably 8 to 24 from the viewpoint of achieving both rust prevention and storage stability.
- 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 the monobasic acid is preferable.
- the number of hydroxyl groups contained in the hydroxycarboxylic acid is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1 from the viewpoint of stability.
- the bonding position of the hydroxyl group in the hydroxycarboxylic acid is arbitrary, but the carboxylic acid ( ⁇ -hydroxy acid) in which the hydroxyl group is bonded to the bonding carbon atom of the carboxylic acid group, or the main chain other than the bonding carbon atom of the carboxylic acid group A carboxylic acid ( ⁇ -hydroxy acid) in which a hydroxyl group is bonded to an end carbon atom is preferable.
- hydroxycarboxylic acid examples include an ⁇ -hydroxy acid represented by the formula (1) and an ⁇ -hydroxy acid represented by the formula (2).
- 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.
- R 2 represents an alkylene group having 1 to 38 carbon atoms or an alkenylene group having 2 to 38 carbon atoms.
- Examples of the alkyl group and alkenyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
- Base Ethenyl group (vinyl group), propenyl group (allyl group), butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group , Hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, hencocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, octacocenyl group, nonacocenyl group
- Examples of the alkylene group and alkenylene group represented by R 2 include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, and dodecylene group.
- a raw material containing such a hydroxycarboxylic acid a lanolin fatty acid obtained by refining a waxy substance adhering to sheep wool by hydrolysis or the like can be preferably used.
- a carboxylic acid having no hydroxyl group may be used in combination.
- the carboxylic acid constituting the partial ester contains both a hydroxycarboxylic acid and a carboxylic acid having no hydroxyl group, the proportion of the hydroxycarboxylic acid in the total amount of the constituting carboxylic acid is preferably 5 to 80% by mass.
- the proportion of the hydroxycarboxylic acid is less than 5% by mass, the rust prevention property tends to be insufficient.
- the proportion of the hydroxycarboxylic acid is more preferably 10% by mass or more, and further preferably 15% by mass or more.
- the proportion of the hydroxycarboxylic acid exceeds 80 mass%, it exists in the tendency for storage stability and the solubility with respect to a base oil to become inadequate.
- the proportion of the hydroxycarboxylic acid is more preferably 60% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
- the carboxylic acid having no hydroxyl group may be a saturated carboxylic acid or an unsaturated carboxylic acid.
- the saturated carboxylic acid may be either a straight chain carboxylic acid or a branched carboxylic acid, but a straight chain carboxylic acid or a branched chain having 1 or 2 carbon atoms, more preferably 1 carbon atom, A branched carboxylic acid having 1 to 3, more preferably 1 to 2, more preferably 1 methyl group is preferred.
- the number of carbon atoms of the saturated carboxylic acid having no hydroxyl group is preferably from 2 to 40, more preferably from 6 to 30, and even more preferably from 8 to 24 from the viewpoint of achieving both rust prevention properties and storage stability.
- 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 a monobasic acid is preferable.
- 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 preferred from the viewpoint of oxidation stability and stain resistance.
- the unsaturated carboxylic acid may be either a linear carboxylic acid or a branched carboxylic acid, or a linear carboxylic acid or a branched chain having 1 or 2 carbon atoms, more preferably 1 carbon atom.
- Preferred is a branched carboxylic acid having ⁇ 3, more preferably 1-2, and even more preferably 1.
- the number of carbon atoms of the unsaturated carboxylic acid 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 preferred 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 a monobasic acid is preferred.
- 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, more preferably 1 to 2, and more preferably 1 from the viewpoint of stability. Particularly preferred.
- 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 oils, 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.
- the proportion of unsaturated carboxylic acid in the constituent carboxylic acid is preferably 5 to 95% by mass.
- the proportion of 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 particularly preferably 35% by mass or more.
- 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.
- Unsaturated carboxylic acids include both unsaturated carboxylic acids having a hydroxyl group and unsaturated carboxylic acids having no hydroxyl group, but the proportion of unsaturated carboxylic acid having no hydroxyl group in the total amount of unsaturated carboxylic acid Is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
- the iodine value of the partial ester is preferably 5 to 75, more preferably 10 to 60 20 to 45 are more preferable.
- the iodine value of the partial ester is less than 5, rust prevention properties and storage stability tend to be lowered.
- 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” 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 a chemical product”.
- Examples of the method for producing the partial ester include the following production methods (i), (ii), and (iii).
- a carboxylic acid having a hydroxyl group and an unsaturated carboxylic acid having no hydroxyl group are mixed, or a saturated carboxylic acid having no hydroxyl group is further mixed so that the carboxylic acid composition of the resulting partial ester satisfies the above conditions.
- a method of mixing and performing a partial esterification reaction of the carboxylic acid mixture and a polyhydric alcohol is performed.
- 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 the carboxylic acid composition is In order to satisfy the conditions, 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
- a method of mixing a partial ester of an acid or a mixture of an unsaturated carboxylic acid having no hydroxyl group and a saturated carboxylic acid having no hydroxyl group A method of mixing a partial ester of an acid or a mixture of an unsaturated carboxylic acid having no hydroxyl group and a saturated carboxylic acid having no hydroxyl group.
- lanolin fatty acid is used as a mixture of hydroxycarboxylic acid and saturated carboxylic acid having no hydroxyl group
- carboxylic acid such as oleic acid is used as unsaturated carboxylic acid having no hydroxyl group.
- Each of these unsaturated carboxylic acids can be preferably used.
- a partial ester (first partial ester) composed of a mixture of a polyhydric alcohol, a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, preferably a lanolin fatty acid, a polyhydric alcohol and a hydroxyl group.
- the content ratio of the unsaturated carboxylic acid, preferably the partial ester composed of oleic acid (second partial ester) is not particularly limited as long as the carboxylic acid composition ratio in the mixture satisfies the above conditions,
- the proportion of the first partial ester in 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 particularly preferably 55 to 65% by mass.
- 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.
- 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 some or all of the acidic groups of the oxidized wax.
- the oxidized wax used as a raw material for the esterified oxidized wax include an oxidized wax;
- examples of alcohols include linear or branched saturated monohydric alcohols having 1 to 20 carbon atoms and linear chains having 1 to 20 carbon atoms. Or branched unsaturated monohydric alcohols, 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 waxy substance adhering to wool with a lanolin fatty acid obtained by purification such as hydrolysis and an alcohol.
- the alcohol used as a raw material for the esterified lanolin fatty acid include the alcohols exemplified in the description of the esterified oxidized wax, and among them, polyhydric alcohols are preferable, and trimethylolpropane, trimethylolethane, sorbitan, pentaerythritol, Glycerin is more preferred.
- alkyl or alkenyl succinic acid ester examples include esters of the alkyl or alkenyl succinic acid with a monohydric alcohol or a dihydric or higher polyhydric alcohol. Among these, esters of monohydric alcohols or dihydric alcohols are preferable.
- the monohydric alcohol may be linear or branched, and may be saturated alcohol or unsaturated alcohol.
- the carbon number of the monohydric alcohol is not particularly limited, but an aliphatic alcohol having 8 to 18 carbon atoms is preferable.
- alkylene glycol and polyoxyalkylene glycol are preferably used.
- alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, and decylene glycol.
- polyoxyalkylene glycol examples include those obtained by homopolymerizing or copolymerizing ethylene oxide, propylene oxide, and butylene oxide.
- the polymerization mode of the oxyalkylene group is not particularly limited, and may be either random copolymerization or block copolymerization.
- the degree of polymerization 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 carboxyl groups of alkyl or alkenyl succinic acid are esterified (complete ester) or only one of the carboxyl groups. Although it may be an esterified monoester (partial ester), a monoester is preferred from the viewpoint of more excellent rust prevention. Among these esters, use of a partial ester of a polyhydric alcohol is particularly preferred from the standpoint of better rust prevention properties. Specifically, pentaerythritol ester of lanolin, sorbitan monooleate, sorbitan isostearate. Etc.
- the amount of ester added is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 6% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, more preferably, based on the total amount of the composition. Is 10% by mass or less. If the amount is too small, sufficient rust preventive properties cannot be obtained. If the amount is too large, the life of the oil agent when a large amount of water is mixed is shortened.
- Component (D) includes (D-1) sarcosine type compound, (D-2) sulfonate, (D-3) amine, (D-4) carboxylic acid, (D-5) carboxylate, (D -6) At least one rust inhibitor selected from the group consisting of paraffin wax, (D-7) oxidized wax salt and (D-8) boron compound.
- the (D-1) sarcosine type compound used in the present embodiment has a structure represented by the following general formula (3), (4) or (5).
- R 3 —CO—NR 4 — (CH 2 ) n —COOX (3) (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, 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
- R 3 represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms.
- 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.
- 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.
- alkyl groups and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Alkyl groups such as heptadecyl group, octadecyl group, nonadecyl group, icosyl group (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, non
- 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.
- 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.
- 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.
- alkyl group or alkenyl group examples include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
- alkyl groups may be linear or branched
- alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group (these alkenyl groups) May be linear or branched, and the position of the double bond is arbitrary).
- 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 an alkyl group having 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.
- 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.
- m represents 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.
- Z represents a residue excluding a hydroxyl group of a polyhydric alcohol having 2 or more valences.
- 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-
- m is an integer of 1 or more
- m ′ is an integer of 0 or more
- 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.
- the sarcosine represented by the above general formulas (3) to (5) it is at least one compound selected from the general formulas (3) and (4) from the viewpoint of more excellent rust prevention properties. preferable. Further, only one compound selected from the general formulas (3) to (5) may be used alone, or a mixture of two or more compounds may be used.
- the content of sarcosine represented by the general formulas (1) to (3) is not particularly limited, but is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass based on the total amount of the composition. %, More preferably 0.3 to 5% by mass.
- the content of the sarcosine is less than the lower limit, rust prevention properties and long-term maintenance properties tend to be insufficient.
- content of the said sarcosine exceeds the said upper limit, it exists in the tendency for the improvement effect of the rust prevention property corresponding to content and its long-term maintenance property not to be acquired.
- Preferable 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 constituting the sulfonate include sodium and potassium. Examples of the alkaline earth metal include magnesium, calcium, and barium. Among these, sodium, potassium, calcium and barium are preferable as the alkali metal and alkaline earth metal, and calcium is particularly preferable.
- examples of the amine include monoamine, polyamine, and alkanolamine.
- Examples of the monoamine include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, monopentylamine, dipentylamine, Pentylamine, monohexylamine, dihexylamine, monoheptylamine, diheptylamine, monooctylamine, dioctylamine, monononylamine, monodecylamine, monoundecylamine, monododecylamine, monotridecylamine, monotetradecyl Amine, monopentadecylamine, monohexadecylamine, monoheptadecylamine, monooctadecylamine, monononadecylamine, monoycosi Amine, monohenicosylamine, mono
- polyamines examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine, dibutylenetriamine, Alkylene polyamines such as tributylenetetramine, tetrabutylenepentamine, pentabylenehexamine; N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-butylethylenediamine, N-pentylethylenediamine, N-hexylethylenediamine, N-heptylethylenediamine, N-octylethylenediamine, N-nonylethylenediamine, N-decylethylenediamine, N-undecyl, N-dode
- the polyamine referred to here also includes polyamines derived from fats and oils (such as beef tallow polyamine).
- alkanolamine examples include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, and tri (n-propanol).
- sulfonic acid a known sulfonic acid produced by a conventional method can be used. Specifically, from sulfonated alkyl aromatic compounds in the lubricating oil fraction of mineral oil, petroleum sulfonic acids such as mahogany acid produced as a by-product during white oil production, or from alkylbenzene production plants used as raw materials for detergents, etc. Synthetic sulfones such as those obtained by alkylating the by-produced polyolefin to benzene, sulfonated alkylbenzenes having linear or branched alkyl groups, and sulfonated alkylnaphthalenes such as dinonylnaphthalene Acid etc. are mentioned.
- dialkylnaphthalenesulfonic acid in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30; the two alkyl groups bonded to the benzene ring are each a linear alkyl group or a side chain methyl group
- a dialkylbenzenesulfonic acid that is a branched alkyl group having 1 and two alkyl groups having a total carbon number of 14 to 30; and a monoalkylbenzenesulfone having 15 or more carbon atoms in the alkyl bonded to the benzene ring It is preferable to use at least one selected from the group consisting of acids.
- a suitable dialkylnaphthalene sulfonic acid in which two alkyl groups bonded to the naphthalene ring have a total carbon number of 14 to 30, and the total carbon number of the two alkyl groups is less than 14, the demulsibility is insufficient. When the other 30 is exceeded, the storage stability of the obtained rust preventive oil composition tends to be lowered.
- Each of the two alkyl groups may be linear or branched. If the total number of carbon atoms in the two alkyl groups is 14 to 30, the number of carbon atoms in each alkyl group is not particularly limited, but the number of carbon atoms in each alkyl group is preferably 6 to 18 respectively.
- a suitable dialkylbenzenesulfonic acid wherein two alkyl groups bonded to the benzene ring are each a branched alkyl group having one linear alkyl group or one side chain methyl group, and the total number of carbon atoms of the two alkyl groups Is a monoalkylbenzene sulfonic acid having a carbon number of 15 or more, as will be described later, a monoalkylbenzene sulfonic acid having an alkyl group having a carbon number of less than 15 can be used.
- the storage stability of the composition tends to decrease.
- an alkylbenzenesulfonic acid having 3 or more alkyl groups is used, the storage stability of the composition tends to decrease.
- a branched alkyl group in which the alkyl group bonded to the benzene ring of the dialkylbenzenesulfonic acid has a branched structure other than the side chain methyl group, such as a branched chain alkyl group having a side chain ethyl group, or two or more branched structures
- the branched alkyl group has a branched chain, such as a branched alkyl group derived from an oligomer of propylene, the human body or the ecosystem may be adversely affected, and the rust prevention property tends to be insufficient. It is in.
- the demulsibility tends to decrease, whereas if it exceeds 30, the storage stability of the composition decreases. Tend to. If the total number of carbon atoms of the two alkyl groups bonded to the benzene ring is 14-30, the number of carbon atoms of each alkyl group is not particularly limited, but the number of carbon atoms of each alkyl group is preferably 6-18.
- a suitable monoalkylbenzenesulfonic acid has one or more alkyl groups bonded to the benzene ring having 15 or more carbon atoms as described above.
- the number of carbon atoms of the alkyl group bonded to the benzene ring is less than 15, the storage stability of the resulting composition tends to decrease.
- the alkyl group bonded to the benzene ring may be linear or branched as long as the carbon number is 15 or more.
- Examples of the sulfonate obtained using the above raw materials include the following. Alkali metal bases such as alkali metal oxides and hydroxides; alkaline earth metal bases such as alkaline earth metal oxides and hydroxides or amines such as ammonia, alkylamines and alkanolamines and sulfonic acids By heating a neutral (normal salt) sulfonate obtained by reacting with 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.
- Alkali metal bases such as alkali metal oxides and hydroxides
- alkaline earth metal bases such as alkaline earth metal oxides and hydroxides
- amines such as ammonia, alkylamines and alkanolamines and sulfonic acids
- the same alkali metal, alkaline earth metal or amine chloride as the target sulfonate is added as a reaction accelerator, or an alkali metal different from the target sulfonate. It is also possible to prepare an alkaline earth metal or amine neutral (normal salt) sulfonate, and then add the same alkali metal alkaline earth metal or amine chloride as the target sulfonate to carry out the exchange reaction. Can be obtained.
- the sulfonate obtained by such a method is not used in the present invention, or the sulfonate obtained by this method is not used. It is preferable to perform sufficient washing treatment such as washing with water.
- the chlorine concentration in the sulfonate is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, further preferably 50 ppm by mass or less, and 25 ppm by mass or less. It is particularly preferable to do this.
- dialkylnaphthalene sulfonate in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30; the two alkyl groups bonded to the benzene ring are each a linear alkyl group or a side group.
- one or more selected from neutral, basic and overbased alkali metal sulfonates and alkaline earth metal sulfonates 50 mg KOH / g, preferably 10 to 30 mg KOH / g neutral or nearly neutral alkali metal or alkaline earth metal sulfonate and / or base number of 50 to 500 mg KOH / g, preferably 200 to 400 mg KOH / g
- basic alkali metal sulfonates or alkaline earth metal sulfonates it is particularly preferred to use basic alkali metal sulfonates or alkaline earth metal sulfonates.
- 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 is preferably 0.1-30, based on the total amount of the composition More preferably, it is 1 to 20, particularly preferably 1.5 to 15.
- the base number refers to a JIS K 2501 “Petroleum Products and Lubricating Oils—Neutralization Value 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
- amine sulfonate, calcium sulfonate, and barium sulfonate are preferable, and alkylene diamine sulfonate and calcium sulfonate are particularly preferable.
- Examples of the rust-preventing component (D-3) amine include the amines exemplified in the description of the sulfonate.
- monoamines are preferable in that they have good stain resistance.
- monoamines having alkylamines, alkyl groups and alkenyl groups, monoamines having alkyl groups and cycloalkyl groups, cycloalkylamines and alkylcyclohexanes are preferred. Alkylamine is more preferred.
- an amine having 3 or more carbon atoms in the amine molecule is preferable, and an amine having 5 or more carbon atoms is more preferable.
- any carboxylic acid can be used, and preferred examples include fatty acids, dicarboxylic acids, hydroxy fatty acids, naphthenic acids, resin acids, oxidized waxes, lanolin fatty acids and the like.
- the number of carbon atoms of the fatty acid is not particularly limited, but is preferably 6 to 24, more preferably 10 to 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 fatty acid.
- fatty acids examples include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid.
- Saturated fatty acids such as icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid; hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, Unsaturated fatty acids such as hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, icosenoic acid, henicosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid; or mixtures thereof; including all substituted isomers of these fatty acids It is done.
- the dicarboxylic acid is preferably a dicarboxylic acid having 2 to 40 carbon atoms, more preferably a dicarboxylic acid having 5 to 36 carbon atoms.
- dimer acid, alkyl or alkenyl succinic acid obtained by dimerizing an unsaturated fatty acid having 6 to 18 carbon atoms is preferably used.
- dimer acid include dimer acid of oleic acid.
- 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.
- hydroxy fatty acid a hydroxy fatty acid having 6 to 24 carbon atoms is preferably used. Further, the hydroxy fatty acid may have one or more hydroxy groups, but those having 1 to 3 hydroxy groups are preferably used. Examples of such hydroxy fatty acids include ricinoleic acid.
- Naphthenic acid refers to carboxylic acids 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 a waxy substance adhering to sheep wool by hydrolysis or the like.
- dicarboxylic acid is preferable, dimer acid is more preferable, and dimer acid of oleic acid is more preferable in terms of rust prevention property, degreasing property, and storage stability.
- Examples of the rust preventive component (D-5) carboxylate include alkali metal salts, alkaline earth metal salts and amine salts of the carboxylic acids.
- Examples of the alkali metal constituting the carboxylate include sodium and potassium, and examples of the alkaline earth metal include barium, calcium and magnesium. Of these, calcium salts are preferably used.
- Examples of the amine include the amines exemplified in the description of the amine. Barium salt may be insufficiently safe for the human body and ecosystem.
- paraffin wax examples include paraffin wax, microcrystalline wax, petrolatum obtained by refining petroleum fractions, and polyolefin wax obtained by synthesis.
- the oxidized wax used as a raw material for the oxidized wax salt is not particularly limited, and examples thereof include oxidized paraffin wax produced by oxidizing wax such as paraffin wax described above.
- the oxidized wax salt is an alkali metal salt
- examples of the alkali metal used as a raw material include sodium and potassium.
- examples of the alkaline earth metal used as a raw material include magnesium, calcium, barium and the like.
- examples of the heavy metal used as a raw material include zinc and lead. Of these, calcium salts are preferred.
- the oxidized wax salt is preferably not a barium salt or a heavy metal salt.
- Examples of the rust-preventing component (D-8) boron compound include potassium borate and calcium borate.
- one of the rust inhibitors of the component (D) may be used alone, or two or more of the same kind of rust inhibitors may be used in combination. Two or more rust inhibitors may be mixed and used.
- rust inhibitor of component (D) sarcosine, sulfonate, or paraffin wax is preferable from the viewpoint of exhibiting more excellent rust preventive properties, and it is more preferable to use these three types in combination.
- alcohols represented by higher aliphatic alcohols phosphoric acid derivatives represented by phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid esters, phosphoric acid, amine salts of phosphorous acid, etc. , Phosphorous acid derivatives and the like can also be contained as rust inhibitors.
- the content in the case of using a rust inhibitor other than carboxylic acid among components (D) is not particularly limited, but from the viewpoint of rust prevention properties, it is preferably 0.1% by mass or more, more preferably, based on the total amount of the composition. It is 0.5 mass% or more, More preferably, it is 1.0 mass% or more.
- the content of the rust inhibitor other than the carboxylic acid in the component (D) is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount of the composition from the viewpoint of storage stability. Preferably it is 10 mass% or less.
- the content in the case of using a carboxylic acid as a rust preventive agent among the component (D) is not particularly limited, but from the viewpoint of rust preventive properties, the total amount of the composition is preferably 0.01% by mass or more, more preferably Is 0.03% by mass or more, more preferably 0.05% by mass or more. If the content of carboxylic acid is less than the lower limit, the effect of improving rust prevention by the addition may be insufficient.
- the content of carboxylic acid is preferably 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1% by mass or less, based on the total amount of the composition. If the carboxylic acid content exceeds the upper limit, the solubility in the base oil becomes insufficient, and the storage stability may be reduced.
- the kinematic viscosity at 40 ° C. of the rust preventive oil composition according to the present embodiment is preferably 2 mm 2 / s or more, more preferably 2.5 mm 2 / s or more, and further preferably 3 mm 2 / s or more. Preferably it is 13 mm ⁇ 2 > / s or less, More preferably, it is 8 mm ⁇ 2 > / s or less, More preferably, it is 7 mm ⁇ 2 > / s or less.
- the kinematic viscosity is less than the lower limit value, the oil film cannot be maintained, so that there is a risk of problems in rust prevention, and when the upper limit value is exceeded, water removability may be reduced.
- a chlorine bleach may be used for the purpose of decolorization.
- a non-chlorine compound such as hydrogen peroxide is used as the bleach. It is preferable to use or not perform a decoloring process.
- chlorine compounds such as hydrochloric acid may be used for the hydrolysis of fats and oils, and 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.
- the chlorine concentration of the rust inhibitor as component (D) is not particularly limited as long as it does not impair the characteristics of the rust preventive oil composition according to this embodiment, but is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less. More preferably, it is 50 ppm or less, and particularly preferably 25 mass ppm or less.
- the rust preventive oil composition according to the present embodiment may further contain other additives as necessary.
- paraffin wax having a remarkable effect of improving the rust-preventing property in an acidic atmosphere
- Phosphate esters such as fate, fats and oils such as lard, fatty acids, higher alcohols, calcium carbonate, potassium borate
- phenolic or amine antioxidants for improving antioxidant performance
- benzotriazole or its derivatives, thiadiazole, Corrosion inhibitors such as benzothiazole for improving corrosion prevention performance
- Wetting agents such as diethylene glycol monoalkyl ether
- Film-forming agents such as acrylic polymer and slack wax
- Antifoaming agents such as methyl silicone, fluorosilicone and polyacrylate Surfactant, Other mixtures thereof.
- content of said other additive is
- the rust preventive oil composition according to the present embodiment does not substantially contain water, does not contain water other than moisture that is naturally absorbed, and is used without intentionally diluting with water.
- the barium, zinc, chlorine and lead contents are each in terms of elements, and preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, based on the total amount of the composition. More preferably, it is 100 mass ppm or less, More preferably, it is 50 mass ppm or less, More preferably, it is 10 mass ppm or less, Most preferably, it is 5 mass ppm or less, More preferably, it is 1 mass ppm 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.
- content of the element in this invention means the value measured by the following method. That is, the content of barium, zinc and lead is measured in accordance with ASTM D 5185-95; the content of chlorine is measured in accordance with the British Petroleum Institute Standard “PROPOSED METHOD AK / 81 Determination of Chlorine Oxidative Method”, respectively. Content (mass ppm) based on the total amount of the composition. The detection limit of each element in the measurement method is usually 1 ppm by mass.
- the rust-preventing oil composition according to this embodiment can achieve all of rust-preventing properties, water-removing properties, degreasing properties, storage stability and detergency at a high level in a balanced manner. It can be suitably used as a stop oil.
- the time for maintaining the rust generation degree A (rust generation degree 0%) is 16 hours or more. Maintains outstanding performance.
- the metal member that is the object to be treated is not particularly limited, and specifically, cold-rolled steel sheets, hot-rolled steel sheets, high-tensile steel sheets, galvanized steel sheets, etc.
- rust prevention oil used for automobile bodies and electrical product bodies, for tinplate Examples thereof include metal plate materials such as an original plate, an aluminum alloy plate, and a magnesium alloy plate, and further bearing components such as a rolling bearing, a tapered rolling bearing, and a needle bearing, a steel material for construction, and a precision component.
- metal plate materials such as an original plate, an aluminum alloy plate, and a magnesium alloy plate
- further bearing components such as a rolling bearing, a tapered rolling bearing, and a needle bearing, a steel material for construction, and a precision component.
- conventional rust prevention oil for such metal members intermediate rust prevention oil used in the process of processing metal members, shipping rust prevention oil used for rust prevention at the time of shipment, press working
- cleaning rust preventive oils used in the cleaning process for removing foreign matters prior to delivery or for removing foreign matters prior to shipment at the metal plate manufacturer, but the cleaning and rust preventing oil composition of the present invention is used for all these applications. can do.
- the method for applying the rust-preventing oil composition according to the present embodiment to the object to be treated is not particularly limited, and for example, it is applied to a metal member by a method such as spraying, dripping, transfer using a felt material, electrostatic oiling or the like. be able to.
- the spray method is preferable because the oil film thickness can be made uniform by coating in a fine mist.
- the application apparatus in the case of applying the spray method is not particularly limited as long as it can atomize the rust preventive oil composition according to the present embodiment. For example, any of an air spray type, an airless spray type, and a hot melt type Is also applicable.
- the rust preventive oil composition according to this embodiment When used as a cleaning oil, a large excess amount of the rust preventive oil composition according to this embodiment is applied to the surface of a metal member by spraying, showering, dip coating, or the like. By refueling, good water removal and subsequent rust prevention can be performed. Furthermore, if necessary, surface cleaning with a roll brush or the like is also performed after the metal processing step, so that the efficiency of removing foreign matters can be increased.
- the rust preventive oil composition it is preferable to recover, circulate, and reuse the cleaning and rust preventive oil composition applied in excess on the metal member. .
- a filter is provided to remove foreign matters. It can be carried out.
- a magnet can be provided in the bottom part of the tank which stores the rust prevention oil composition which concerns on this embodiment, and foreign materials, such as abrasion powder, can also be adsorbed
- the properties of the oil used are periodically measured by measuring the kinematic viscosity and density, copper plate corrosion test, rust-preventing property test, etc. It is preferable to manage and perform oil renewal, drain disposal, tank cleaning, oil purification operation, etc. as necessary.
- the oil For discarded oils, use the oil as it is, or dilute with a solvent or low-viscosity base oil, and use it in a line that requires less performance for cleaning and rust prevention oil composition than the line used before disposal. As a result, the total amount of oil used can be reduced.
- the rust preventive oil composition according to the present embodiment is stored in the tank, it is preferably replenished according to the amount of decrease in the composition in the tank. In that case, it may not necessarily be the same composition as the composition filled in the initial stage, and a composition or the like in which the additive for increasing the performance desired to be strengthened may be replenished as occasion demands. Or conversely, the cleaning ability of the cleaning and rust preventive oil composition may be maintained by replenishing a composition having a reduced viscosity by a method such as reducing the content of the high viscosity base oil.
- the metal plate When the rust preventive oil composition according to the present embodiment is used in a cleaning process for removing foreign matters prior to shipment in a metal plate manufacturer, the metal plate is wound up in a coil shape immediately after the cleaning process, or stacked as a sheet material. Can be shipped. According to this method, there is a merit that the amount of foreign matter attached is small and cleaning can be performed easily and reliably even when a cleaning process using a cleaning rust prevention oil is performed immediately before the pressing process in pressing. As a matter of course, a rust-preventing treatment may be performed in two stages by providing a step of applying rust-preventing oil again after the step of washing with the cleaning rust-preventing oil at the steel plate manufacturing site.
- Examples 1 to 42, Comparative Examples 1 to 15 In Examples 1 to 42 and Comparative Examples 1 to 15, rust prevention oil compositions having the compositions shown in Tables 1 to 6 were prepared using the components shown below.
- Component A1 Mineral oil having a kinematic viscosity at 40 ° C. of 0.9 mm 2 / s (aromatic content: 0.1% by mass or less)
- A2 Mineral oil having a kinematic viscosity at 40 ° C. of 1.6 mm 2 / s (aromatic content: 0.1% by mass or less)
- A3 Mineral oil having a kinematic viscosity of 1.9 mm 2 / s at 40 ° C.
- A4 Mineral oil with a kinematic viscosity at 40 ° C. of 8.4 mm 2 / s
- A5 Mineral oil with a kinematic viscosity at 40 ° C. of 23 mm 2 / s
- A6 Mineral oil with a kinematic viscosity at 40 ° C. of 68 mm 2 / s
- A7 Kinematic at 40 ° C. mineral oil having a viscosity of 195mm 2 / s
- A8 40 kinematic viscosity at ° C.
- B1 C8 C8 alkylamine salts of fatty acids
- B2 C18 alkylamine salt of C8 fatty acid
- B3 C8 alkylamine salt of C18 fatty acid
- B4 C18 alkylamine salt of C18 fatty acid
- Component C1 Lanolin fatty acid partial ester of pentaerythritol
- C2 Sorbitan monoisostearate
- C3 Sorbitan mono Olate
- C4 trimethylolpropane monooleate
- D1 oleoi Sarcosine (N-Methyloleamidoacetic acid)
- D2 Ethylenediamine sulfonate
- D3 Basic Ca sulfonate (base number: 95 mgKOH / g)
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Abstract
Description
40℃における動粘度が6mm2/s以下の鉱油である第1の鉱油と、
40℃における動粘度が250mm2/s以上の鉱油である第2の鉱油と、
脂肪酸アミン塩と、
エステルと、
ザルコシン型化合物、ノニオン系界面活性剤、スルホン酸塩、アミン、カルボン酸、脂肪酸アミン塩、カルボン酸塩、パラフィンワックス、酸化ワックス塩及びホウ素化合物からなる群から選ばれる1種以上のさび止め剤と、
を含有する。
(A-1)40℃における動粘度が6mm2/s以下の鉱油(第1の鉱油)と、
(A-2)40℃における動粘度が250mm2/s以上の鉱油(第2の鉱油)と、
(B)脂肪酸アミン塩と、
(C)エステルと、
(D)ザルコシン型化合物、ノニオン系界面活性剤、スルホン酸塩、アミン、カルボン酸、脂肪酸アミン塩、カルボン酸塩、パラフィンワックス、酸化ワックス塩及びホウ素化合物からなる群から選ばれる1種以上のさび止め剤と、
を含有する。
を含む)等のN-アルケニルエチレンジアミン;N-アルキルジエチレントリアミン、N-アルケニルジエチレントリアミン、N-アルキルトリエチレンテトラミン、N-アルケニルトリエチレンテトラミン、N-アルキルテトラエチレンペンタミン、N-アルケニルテトラエチレンペンタミン、N-アルキルペンタエチレンヘキサミン、N-アルケニルペンタエチレンヘキサミン、N-アルキルプロピレンジアミン、N-アルケニルプロピレンジアミン、N-アルキルジプロピレントリアミン、N-アルケニルジプロピレントリアミン、N-アルキルトリプロピレンテトラミン、N-アルケニルトリプロピレンテトラミン、N-アルキルテトラプロピレンペンタミン、N-アルケニルテトラプロピレンペンタミン、N-アルキルペンタプロピレンヘキサミン、N-アルケニルペンタプロピレンヘキサミン、N-アルキルブチレンジアミン、N-アルケニルブチレンジアミン、N-アルキルジブチレントリアミン、N-アルケニルジブチレントリアミン、N-アルキルトリブチレンテトラミン、N-アルケニルトリブチレンテトラミン、N-アルキルテトラブチレンペンタミン、N-アルケニルテトラブチレンペンタミン、N-アルキルペンタブチレンヘキサミン、N-アルケニルペンタブチレンヘキサミン等のN-アルキルまたはN-アルケニルアルキレンポリアミン;等が挙げられる。また、このポリアミンには牛脂ポリアミン等に代表されるような、油脂から誘導されるポリアミンも含まれる。上記アルカノールアミンとしては、具体的には例えば、モノメタノールアミン、ジメタノールアミン、トリメタノールアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ(n-プロパノール)アミン、ジ(n-プロパノール)アミン、トリ(n-プロパノール)アミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、モノブタノールアミン(全ての異性体を含む)、ジブタノールアミン(全ての異性体を含む)、トリブタノールアミン(全ての異性体を含む)、モノペンタノールアミン(全ての異性体を含む)、ジペンタノールアミン(全ての異性体を含む)、トリペンタノールアミン(全ての異性体を含む)、モノヘキサノールアミン(全ての異性体を含む)、ジヘキサノールアミン(全ての異性体を含む)、モノヘプタノールアミン(全ての異性体を含む)、ジヘプタノールアミン(全ての異性体を含む)、モノオクタノールアミン(全ての異性体を含む)、モノノナノールアミン(全ての異性体を含む)、モノデカノールアミン(全ての異性体を含む)、モノウンデカノールアミン(全ての異性体を含む)、モノドデカノールアミン(全ての異性体を含む)、モノトリデカノールアミン(全ての異性体を含む)、モノテトラデカノールアミン(全ての異性体を含む)、モノペンタデカノールアミン(全ての異性体を含む)、モノヘキサデカノールアミン(全ての異性体を含む)、ジエチルモノエタノールアミン、ジエチルモノプロパノールアミン(全ての異性体を含む)、ジエチルモノブタノールアミン(全ての異性体を含む)、ジエチルモノペンタノールアミン(全ての異性体を含む)、ジプロピルモノエタノールアミン(全ての異性体を含む)、ジプロピルモノプロパノールアミン(全ての異性体を含む)、ジプロピルモノブタノールアミン(全ての異性体を含む)、ジプロピルモノペンタノールアミン(全ての異性体を含む)、ジブチルモノエタノールアミン(全ての異性体を含む)、ジブチルモノプロパノールアミン(全ての異性体を含む)、ジブチルモノブタノールアミン(全ての異性体を含む)、ジブチルモノペンタノールアミン(全ての異性体を含む)、モノエチルジエタノールアミン、モノエチルジプロパノールアミン(全ての異性体を含む)、モノエチルジブタノールアミン(全ての異性体を含む)、モノエチルジペンタノールアミン(全ての異性体を含む)、モノプロピルジエタノールアミン(全ての異性体を含む)、モノプロピルジプロパノールアミン(全ての異性体を含む)、モノプロピルジブタノールアミン(全ての異性体を含む)、モノプロピルジペンタノールアミン(全ての異性体を含む)、モノブチルジエタノールアミン(全ての異性体を含む)、モノブチルジプロパノールアミン(全ての異性体を含む)、モノブチルジブタノールアミン(全ての異性体を含む)、モノブチルジペンタノールアミン(全ての異性体を含む)等が挙げられる。上記したアミンの中でも、冷凍システムへの影響が少ないことから、モノアミンが好ましく、モノアミンの中でも特にアルキルアミン、アルキル基及びアルケニル基を有するモノアミン、アルキル基及びシクロアルキル基を有するモノアミン、シクロアルキルアミン並びにアルキルシクロアルキルアミンがより好ましい。また、耐ステイン性の点から、アミン分子中の合計炭素数が3以上のアミンが好ましく、合計炭素数が5以上のアミンがより好ましい。
(C-1)多価アルコールの部分エステルとは、多価アルコール中の水酸基の少なくとも1個以上がエステル化されておらず水酸基のままで残っているエステルであり、その原料である多価アルコールとしては任意のものが使用可能であるが、分子中の水酸基の数は好ましくは2~10、より好ましくは3~6であり、且つ炭素数が2~20、より好ましくは3~10である多価アルコールが好適に使用される。これらの多価アルコールの中でも、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトールおよびソルビタンからなる群より選ばれる少なくとも1種の多価アルコールを用いることが好ましく、ペンタエリスリトールを用いることがより好ましい。
(i)多価アルコールとヒドロキシカルボン酸との、またはヒドロキシカルボン酸と水酸基を有さない飽和カルボン酸との混合物との部分エステルと、多価アルコールと水酸基を有さない不飽和カルボン酸との、または水酸基を有さない不飽和カルボン酸と水酸基を有さない飽和カルボン酸との混合物との部分エステルとを、両者の混合物におけるカルボン酸組成が上記条件を満たすように混合する方法。
(ii)得られる部分エステルのカルボン酸組成が上記条件を満たすように、水酸基を有するカルボン酸と水酸基を有さない不飽和カルボン酸とを混合し、あるいは水酸基を有さない飽和カルボン酸を更に混合し、当該カルボン酸混合物と多価アルコールとの部分エステル化反応を行う方法。
(iii)ヒドロキシカルボン酸と水酸基を有さない不飽和カルボン酸との混合物との、あるいはこれらのカルボン酸と水酸基を有さない飽和カルボン酸との混合物との部分エステルに、カルボン酸組成が上記条件を満たすように、多価アルコールとヒドロキシカルボン酸との、もしくはヒドロキシカルボン酸と水酸基を有さない飽和カルボン酸との混合物との部分エステル、または多価アルコールと水酸基を有さない不飽和カルボン酸との、もしくは水酸基を有さない不飽和カルボン酸と水酸基を有さない飽和カルボン酸との混合物との部分エステルを混合する方法。
R3-CO-NR4-(CH2)n-COOX (3)
(式中、R3は炭素数6~30のアルキル基又は炭素数6~30のアルケニル基、R4は炭素数1~4のアルキル基、Xは水素原子、炭素数1~30のアルキル基又は炭素数1~30のアルケニル基、nは1~4の整数を示す。)
[R3-CO-NR4-(CH2)n-COO]mY (4)
(式中、R3は炭素数6~30のアルキル基又は炭素数6~30のアルケニル基、R4は炭素数1~4のアルキル基、Yはアルカリ金属又はアルカリ土類金属、nは1~4の整数、mはYがアルカリ金属の場合は1、アルカリ土類金属の場合は2を示す。)
[R3-CO-NR4-(CH2)n-COO]m-Z-(OH)m (5)
(式中、R3は炭素数6~30のアルキル基又は炭素数6~30のアルケニル基、R4は炭素数1~4のアルキル基、Zは2価以上の多価アルコールの水酸基を除いた残基、mは1以上の整数、m’は0以上の整数、m+m’はZの価数、nは1~4の整数を示す。)
スルホン酸塩を構成するアルカリ金属としては、ナトリウム、カリウム等が挙げられる。また、アルカリ土類金属としては、マグネシウム、カルシウム、バリウム等が挙げられる。中でも、アルカリ金属およびアルカリ土類金属としては、ナトリウム、カリウム、カルシウム及びバリウムが好ましく、カルシウムが特に好ましい。
ノビニルアミン、ジビニルアミン、トリビニルアミン、モノプロペニルアミン、ジプロペニルアミン、トリプロペニルアミン、モノブテニルアミン、ジブテニルアミン、トリブテニルアミン、モノペンテニルアミン、ジペンテニルアミン、トリペンテニルアミン、モノヘキセニルアミン、ジヘキセニルアミン、モノヘプテニルアミン、ジヘプテニルアミン、モノオクテニルアミン、ジオクテニルアミン、モノノネニルアミン、モノデセニルアミン、モノウンデセニルアミン、モノドデセニルアミン、モノトリデセニルアミン、モノテトラデセニルアミン、モノペンタデセニルアミン、モノヘキサデセニルアミン、モノヘプタデセニルアミン、モノオクタデセニルアミン、モノノナデセニルアミン、モノイコセニルアミン、モノヘンイコセニルアミン、モノドコセニルアミン、モノトリコセニルアミン等のアルケニルアミン;
ジメチル(ビニル)アミン、ジメチル(プロペニル)アミン、ジメチル(ブテニル)アミン、ジメチル(ペンテニル)アミン、ジメチル(ヘキセニル)アミン、ジメチル(ヘプテニル)アミン、ジメチル(オクテニル)アミン、ジメチル(ノネニル)アミン、ジメチル(デセニル)アミン、ジメチル(ウンデセニル)アミン、ジメチル(ドデセニル)アミン、ジメチル(トリデセニル)アミン、ジメチル(テトラデセニル)アミン、ジメチル(ペンタデセニル)アミン、ジメチル(ヘキサデセニル)アミン、ジメチル(ヘプタデセニル)アミン、ジメチル(オクタデセニル)アミン、ジメチル(ノナデセニル)アミン、ジメチル(イコセニル)アミン、ジメチル(ヘンイコセニル)アミン、ジメチル(トリコセニル)アミン等のアルキル基およびアルケニル基を有するモノアミン;
モノベンジルアミン、(1-フェネチル)アミン、(2-フェネチル)アミン(別名:モノフェネチルアミン)、ジベンジルアミン、ビス(1-フェネチル)アミン、ビス(2-フェネチル)アミン(別名:ジフェネチルアミン)等の芳香族置換アルキルアミン;モノシクロペンチルアミン、ジシクロペンチルアミン、トリシクロペンチルアミン、モノシクロヘキシルアミン、ジシクロヘキシルアミン、モノシクロヘプチルアミン、ジシクロヘプチルアミン等の炭素数5~16のシクロアルキルアミン;ジメチル(シクロペンチル)アミン、ジメチル(シクロヘキシル)アミン、ジメチル(シクロヘプチル)アミン等のアルキル基およびシクロアルキル基を有するモノアミン;(メチルシクロペンチル)アミン、ビス(メチルシクロペンチル)アミン、(ジメチルシクロペンチル)アミン、ビス(ジメチルシクロペンチル)アミン、(エチルシクロペンチル)アミン、ビス(エチルシクロペンチル)アミン、(メチルエチルシクロペンチル)アミン、ビス(メチルエチルシクロペンチル)アミン、(ジエチルシクロペンチル)アミン、(メチルシクロヘキシル)アミン、ビス(メチルシクロヘキシル)アミン、(ジメチルシクロヘキシル)アミン、ビス(ジメチルシクロヘキシル)アミン、(エチルシクロヘキシル)アミン、ビス(エチルシクロヘキシル)アミン、(メチルエチルシクロヘキシル)アミン、(ジエチルシクロヘキシル)アミン、(メチルシクロヘプチル)アミン、ビス(メチルシクロヘプチル)アミン、(ジメチルシクロヘプチル)アミン、(エチルシクロヘプチル)アミン、(メチルエチルシクロヘプチル)アミン、(ジエチルシクロヘプチル)アミン等のアルキルシクロアルキルアミンが挙げられ、これらモノアミンの全ての置換異性体も挙げられる。ここでいうモノアミンには、油脂から誘導される牛脂アミン等のモノアミンも含まれる。
N-メチルエチレンジアミン、N-エチルエチレンジアミン、N-プロピルエチレンジアミン、N-ブチルエチレンジアミン、N-ペンチルエチレンジアミン、N-ヘキシルエチレンジアミン、N-ヘプチルエチレンジアミン、N-オクチルエチレンジアミン、N-ノニルエチレンジアミン、N-デシルエチレンジアミン、N-ウンデシル、N-ドデシルエチレンジアミン、N-トリデシルエチレンジアミン、N-テトラデシルエチレンジアミン、N-ペンタデシルエチレンジアミン、N-ヘキサデシルエチレンジアミン、N-ヘプタデシルエチレンジアミン、N-オクタデシルエチレンジアミン、N-ノナデシルエチレンジアミン、N-イコシルエチレンジアミン、N-ヘンイコシルエチレンジアミン、N-ドコシルエチレンジアミン、N-トリコシルエチレンジアミン等のN-アルキルエチレンジアミン;
N-ビニルエチレンジアミン、N-プロペニルエチレンジアミン、N-ブテニルエチレンジアミン、N-ペンテニルエチレンジアミン、N-ヘキセニルエチレンジアミン、N-ヘプテニルエチレンジアミン、N-オクテニルエチレンジアミン、N-ノネニルエチレンジアミン、N-デセニルエチレンジアミン、N-ウンデセニル、N-ドデセニルエチレンジアミン、N-トリデセニルエチレンジアミン、N-テトラデセニルエチレンジアミン、N-ペンタデセニルエチレンジアミン、N-ヘキサデセニルエチレンジアミン、N-ヘプタデセニルエチレンジアミン、N-オクタデセニルエチレンジアミン、N-ノナデセニルエチレンジアミン、N-イコセニルエチレンジアミン、N-ヘンイコセニルエチレンジアミン、N-ドコセニルエチレンジアミン、N-トリコセニルエチレンジアミン等のN-アルケニルエチレンジアミン;
N-アルキルジエチレントリアミン、N-アルケニルジエチレントリアミン、N-アルキルトリエチレンテトラミン、N-アルケニルトリエチレンテトラミン、N-アルキルテトラエチレンペンタミン、N-アルケニルテトラエチレンペンタミン、N-アルキルペンタエチレンヘキサミン、N-アルケニルペンタエチレンヘキサミン、N-アルキルプロピレンジアミン、N-アルケニルプロピレンジアミン、N-アルキルジプロピレントリアミン、N-アルケニルジプロピレントリアミン、N-アルキルトリプロピレンテトラミン、N-アルケニルトリプロピレンテトラミン、N-アルキルテトラプロピレンペンタミン、N-アルケニルテトラプロピレンペンタミン、N-アルキルペンタプロピレンヘキサミン、N-アルケニルペンタプロピレンヘキサミン、N-アルキルブチレンジアミン、N-アルケニルブチレンジアミン、N-アルキルジブチレントリアミン、N-アルケニルジブチレントリアミン、N-アルキルトリブチレンテトラミン、N-アルケニルトリブチレンテトラミン、N-アルキルテトラブチレンペンタミン、N-アルケニルテトラブチレンペンタミン、N-アルキルペンタブチレンヘキサミン、N-アルケニルペンタブチレンヘキサミン等のN-アルキルまたはN-アルケニルアルキレンポリアミンが挙げられ、これらポリアミンの全ての置換異性体も挙げられる。また、ここでいうポリアミンには油脂から誘導されるポリアミン(牛脂ポリアミン等)も含まれる。
アルカノールアミンとしては、例えば、モノメタノールアミン、ジメタノールアミン、トリメタノールアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ(n-プロパノール)アミン、ジ(n-プロパノール)アミン、トリ(n-プロパノール)アミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、モノブタノールアミン、ジブタノールアミン、トリブタノールアミン、モノペンタノールアミン、ジペンタノールアミン、トリペンタノールアミン、モノヘキサノールアミン、ジヘキサノールアミン、モノヘプタノールアミン、ジヘプタノールアミン、モノオクタノールアミン、モノノナノールアミン、モノデカノールアミン、モノウンデカノールアミン、モノドデカノールアミン、モノトリデカノールアミン、モノテトラデカノールアミン、モノペンタデカノールアミン、モノヘキサデカノールアミン、ジエチルモノエタノールアミン、ジエチルモノプロパノールアミン、ジエチルモノブタノールアミン、ジエチルモノペンタノールアミン、ジプロピルモノエタノールアミン、ジプロピルモノプロパノールアミン、ジプロピルモノブタノールアミン、ジプロピルモノペンタノールアミン、ジブチルモノエタノールアミン、ジブチルモノプロパノールアミン、ジブチルモノブタノールアミン、ジブチルモノペンタノールアミン、モノエチルジエタノールアミン、モノエチルジプロパノールアミン、モノエチルジブタノールアミン、モノエチルジペンタノールアミン、モノプロピルジエタノールアミン、モノプロピルジプロパノールアミン、モノプロピルジブタノールアミン、モノプロピルジペンタノールアミン、モノブチルジエタノールアミン、モノブチルジプロパノールアミン、モノブチルジブタノールアミン、モノブチルジペンタノールアミン、モノシクロヘキシルモノエタノールアミン、モノシクロヘキシルジエタノールアミン、モノシクロヘキシルモノプロパノールアミン、モノシクロヘキシルジプロパノールアミンが挙げられ、これらアルカノールアミンの全ての置換異性体も挙げられる。
カルボン酸の含有量が前記下限値未満であると、その添加によるさび止め性向上効果が不十分となる恐れがある。また、カルボン酸の含有量は、組成物全量を基準として、好ましくは2質量%以下、より好ましくは1.5質量%以下、更に好ましくは1質量%以下である。カルボン酸の含有量が前記上限値を超えると、基油に対する溶解性が不十分となり、貯蔵安定性が低下する恐れがある。
なお、本発明における元素の含有量とは、以下の方法によって測定される値をいう。すなわち、バリウム、亜鉛および鉛の含有量とは、ASTM D 5185-95;塩素の含有量とは、英国石油協会規格「PROPOSED METHOD AK/81 Determination of chlorine Microcoulometry oxidative method」にそれぞれ準拠して測定される組成物全量を基準とした含有量(質量ppm)を意味する。上記測定方法における各元素の検出限界は通常1質量ppmである。
被処理体である金属製部材は特に制限されず、具体的には、自動車ボディや電気製品ボディとなる冷延鋼板、熱延鋼板、高張力鋼板、亜鉛めっき鋼板等の表面処理鋼板、ブリキ用原板、アルミニウム合金板、マグネシウム合金板等の金属製板材、更には転がり軸受、テーパー転がり軸受、ニードル軸受等の軸受部品、建築用鋼材、精密部品等が挙げられる。
このような金属製部材に対する従来のさび止め油としては、金属製部材の加工工程等の過程で用いられる中間さび止め油、出荷時のさび止めのために用いられる出荷さび止め油、プレス加工に供する前の異物除去または金属板製造メーカーにおいて出荷に先立つ異物除去のための洗浄工程で用いられる洗浄さび止め油などがあるが、本発明の洗浄兼さび止め油組成物はこれらすべての用途に使用することができる。
実施例1~42及び比較例1~15においては、それぞれ以下に示す成分を用いて、表1~6に示す組成を有するさび止め油組成物を調製した。
(A)成分
A1:40℃における動粘度が0.9mm2/sの鉱油(芳香族分:0.1質量%以下)
A2:40℃における動粘度が1.6mm2/sの鉱油(芳香族分:0.1質量%以下)
A3:40℃における動粘度が1.9mm2/sの鉱油(芳香族分:4.8質量%)
A4:40℃における動粘度が8.4mm2/sの鉱油
A5:40℃における動粘度が23mm2/sの鉱油
A6:40℃における動粘度が68mm2/sの鉱油
A7:40℃における動粘度が195mm2/sの鉱油
A8:40℃における動粘度が461mm2/sの鉱油
A9:40℃における動粘度:586mm2/sの鉱油
(B)成分
B1:C8脂肪酸のC8アルキルアミン塩
B2:C8脂肪酸のC18アルキルアミン塩
B3:C18脂肪酸のC8アルキルアミン塩
B4:C18脂肪酸のC18アルキルアミン塩
(C)成分
C1:ペンタエリスリトールのラノリン脂肪酸部分エステル
C2:ソルビタンモノイソステアレート
C3:ソルビタンモノオレート
C4:トリメチロールプロパンモノオレート
(D)成分
D1:オレオイルザルコシン(N-Methyloleamidoacetic acid)
D2:エチレンジアミンスルホネート
D3:塩基性Caスルホネート(塩基価:95mgKOH/g)
D4:パラフィンワックス
JIS K2246「さび止め油」中性塩水噴霧試験に準拠して評価を実施した。なお、試験片の研磨はJIS K2246「さび止め油」水置換試験方法に準拠し、A,P100の研磨材で行った。試験を実施する前に、予め試験片を水平に保った状態で水道水に5分間浸漬しその後直ちに水平に保った状態でさび止め油に5秒間浸漬した後に、水平に保った状態で取り出し50℃、95%の恒温恒湿槽内で3時間静置した。その後、試験法に準拠して中性塩水噴霧試験を実施した。さびが発生するまでの時間(h)を測定して評価し、評価は所定の時間毎(16,24,36,48時間)に行った。評価はJIS法に基づき試験数3で実施した。得られた結果を表1~6に示す。
なお、油剤の安定性が悪く分離が認められるようなものは十分に攪拌した状態で試験に供した。
本評価では水除去性能が不十分であると水に起因するさびが発生するため、油剤そのもののさび止め性能と併せ水除去性を評価することができる。
油剤1リットルにイオン交換水1リトルを加え、5Lビーカ内にて全体がけん濁する程度の強度にて10時間攪拌した(1日目)。その後静置し、翌日も同様の操作を実施した。これを10回繰り返した。1日目、3日目、5日目、10日目に攪拌終了後、油層を分別して試験油とし、JIS K2246の中性塩水噴霧試験を実施しさび止め性能の低下度合いを比較した。さび止め性の評価は24時間後の試験片の状態を観察して評価した。得られた結果を表1~6に示す。
さび止め油組成物を調製後、45℃に調整した恒温槽中に240時間保持し、油剤の分離の有無を目視で評価した。分離しない場合を、「無」、分離した場合を「有」とした。得られた結果を表1~6に示す。
JIS K2283に準拠して、さび止め油組成物の40℃における動粘度を測定した。得られた結果を表1~6に示す。
Claims (4)
- 40℃における動粘度が6mm2/s以下の鉱油である第1の鉱油と、
40℃における動粘度が250mm2/s以上の鉱油である第2の鉱油と、
脂肪酸アミン塩と、
エステルと、
ザルコシン型化合物、ノニオン系界面活性剤、スルホン酸塩、アミン、カルボン酸、脂肪酸アミン塩、カルボン酸塩、パラフィンワックス、酸化ワックス塩及びホウ素化合物からなる群から選ばれる1種以上のさび止め剤と、
を含有するさび止め油組成物。 - 40℃における動粘度が10mm2/s以上120mm2/s以下の鉱油である第3の鉱油をさらに含有する、請求項1に記載のさび止め油組成物。
- 前記第1の鉱油の芳香族分含有量が、前記第1の鉱油の全量を基準として、3質量%以下である、請求項1又は2に記載のさび止め油組成物。
- JIS K 2246「さび止め油」で規定されている中性塩水噴霧試験において、さび発生度がA級(さび発生度が0%)を維持する時間が16時間以上である、請求項1~3のいずれか一項に記載のさび止め油組成物。
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