JPH0790636A - Corrosive preventive composition - Google Patents

Abstract

PURPOSE:To produce a corrosive preventive composition showing excellent corrosion preventive performance in an acidic atmosphere by incorporating a specific ratio of neutral alkali metal sulfonate, phenate, oxidized wax or the like into a mineral oil or the like of a base oil and controlling the kinematic viscosity, total base number or the like. CONSTITUTION:The corrosion preventive composition 1-150mm<2>/s in kinematic viscosity at 40 deg.C, 1-30mgKOH/g in base number and 2-20 in the ratio of total base number (mgKOH/g)total acid number (mgKOH/g) is produced by incorporating 0.1-20wt.% neutral alkali metal and/or alkaline earth metal sulfonate, 0.1-20wt.% alkali metal or alkaline earth metal organic acid salt of at least one kind of phenate or salicylate, which is 20-500mgKOH/g in total base number, 1-20wt.% at least one kind of selected from the oxidized wax and its derivative, a partial ester of polyhydric alcohol and a lanolin fatty acid derivative as an essential components into the mineral oil or a synthetic oil used as the base oil.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust preventive oil composition, and more specifically, it shows excellent rust preventive performance even in an acidic atmosphere, and the performance is maintained even after storage under hot and humid conditions. The present invention relates to a rust preventive oil composition having excellent storage stability.

[0002]

2. Description of the Related Art Conventionally, a rust preventive oil composition having excellent rust preventive performance can be obtained by combining a neutral metal sulfonate with an oxidized wax, a partial ester of a polyhydric alcohol, a lanolin fatty acid derivative or the like. Was known. However, with the recent concentration of industries and populations in urban areas, the amount of acidic components released into the atmosphere from factories, automobiles, incinerators, etc. has increased, and the performance of conventionally known rust preventive oils as described above is not sufficient. It has become necessary to develop a rust preventive oil that is sufficient and has excellent rust preventive performance.

[0003]

As a result of repeated studies to solve the above problems, the present inventors have decided to use a mineral oil or a synthetic oil as a base oil, and add a neutral metal sulfonate and a specified base number to the base oil. Organic acid metal salt consisting of at least one of phenate and salicylate, and a specific amount of at least one of oxidized waxes, partial ester of polyhydric alcohol and lanolin fatty acid derivative, and total kinematic viscosity of the composition By adjusting the base number and the ratio of total base number / total acid number to be in a specific range, it has excellent rust preventive performance even in an acidic atmosphere and even in a thin film thickness. It was found that a rust preventive oil composition having excellent storage stability, which is maintained even after storage under high temperature and high humidity conditions, can be obtained, and the present invention It has been completed.

The present invention uses a mineral oil and / or a synthetic oil as a base oil, and on the basis of the total amount of the composition, (1) 0.1 to 20% by weight of a neutral alkali metal and / or alkaline earth metal sulfonate, 2) At least one alkali metal and / or alkaline earth metal organic acid salt having a total base number of 20 to 500 mgKOH / g selected from phenates and salicylates 0.1
To 20% by weight, and (3) at least 1 selected from the following (a) to (c):
0.1 to 20% by weight of a compound of the type, (a) an oxidized wax and / or its derivative, (b) a partial ester of a polyhydric alcohol, (c) a lanolin fatty acid derivative as an essential component, and at 40 ° C. of the composition. Has a kinematic viscosity of 1 to 150 mm ² / s and a total base number of 1 to 30 mg KO
The present invention provides a rust preventive oil composition, which has a ratio of H / g and total base number (mgKOH / g) / total acid number (mgKOH / g) of 2 to 20.

The contents of the present invention will be described in more detail below. The base oil of the rust preventive oil composition of the present invention is a mineral oil and / or
Or synthetic oil. The mineral oil and / or synthetic oil here is not particularly limited other than the above kinematic viscosity, and any one can be used alone as long as it is used as a base oil of a normal lubricating oil, It can also be used in the form of a mixture of two or more kinds.

As the mineral oil base oil, for example, a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and vacuum distillation is subjected to solvent degassing, solvent extraction, hydrogenolysis, solvent dewaxing, catalytic dewaxing. Oils such as paraffin oils and naphthene oils that have been refined by appropriately combining refining treatments such as hydrorefining, sulfuric acid washing, and clay treatment can be used.

Examples of synthetic base oils include
Poly α-olefin (polybutene, 1-octene oligomer, 1-decene oligomer, etc.), alkylbenzene, alkylnaphthalene, diester (ditridecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di2-ethylhexyl sebacate) Etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-
Ethyl hexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, polyphenyl ether, etc. can be used. These base oils may be used alone or in combination of two or more.

The mineral oil and / or synthetic oil may have any kinematic viscosity. As will be described later, as long as the final composition has a kinematic viscosity at 40 ° C. of 1 to 150 mm ² / s, any kinematic viscosity can be used, but usually 4
Kinematic viscosity at 0 ° C is 0.7-500 mm ² / s, preferably 1
It is preferable to use mineral oil and / or synthetic oil of -80 mm ² / s alone or in a mixture of two or more kinds.

The component (1) which is an essential additive component constituting the rust preventive oil composition of the present invention is an alkali metal and / or alkaline earth metal neutral sulfonate.

As used herein, the neutral alkali metal and / or alkaline earth metal sulfonate has a molecular weight of about 10
Alkali metal neutral salt (normal salt), alkaline earth metal neutral salt (normal salt) of alkylaromatic sulfonic acid obtained by sulfonation of 0 to 1500, preferably 200 to 700 alkylaromatic compound, Or, it means a mixture thereof, and examples of the alkali metal include, for example, sodium and potassium, and examples of the alkaline earth metal include, for example, magnesium, calcium, and barium. Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum sulfonic acid and synthetic sulfonic acid.

As the petroleum sulfonic acid referred to herein, generally used are those obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, and so-called mahogany acid produced as a by-product during the production of white oil.

The synthetic sulfonic acid is, for example, an alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant as a raw material for detergents or obtained by alkylating a polyolefin into benzene. Sulfonated compounds, or sulfonated alkylnaphthalene such as dinonylnaphthalene are used. The sulfonating agent used for sulfonating these alkyl aromatic compounds is not particularly limited, and fuming sulfuric acid or sulfuric anhydride is usually used.

The component (1) of the present invention is a neutral (normal salt) obtained by directly reacting the above alkylaromatic sulfonic acid with an alkali metal oxide such as sodium or potassium or a base such as hydroxide. ) Alkali metal sulfonates and alkylaromatic sulfonic acids are directly reacted with bases such as oxides and hydroxides of alkaline earth metals such as magnesium, calcium and barium, or once converted into alkali metal neutral salts to give alkali. Neutral (normal salt) obtained by substituting with an earth metal salt
Alkaline earth metal sulfonates, or mixtures thereof are used, but these are usually 0 to 7 mgKOH /
g, preferably 0-5 mg KOH / g total base number (JIS K 2501
According to the perchloric acid method specified in 1).

In the present invention, among the above-mentioned neutral alkali metal and / or alkaline earth metal sulfonates as the component (1), it is preferable to use neutral barium sulfonate because of its excellent rust-preventing performance. .

The content of the (1) neutral alkali metal and / or alkaline earth metal sulfonate in the present invention is 0.1 to 20% by weight, preferably 3 to 15% by weight, based on the total amount of the composition. When the component (1) is not used and the content of the component (1) is less than 0.1% by weight, the rust preventive performance is poor, while when the content exceeds 20% by weight, the effect is It is not preferable because it becomes saturated and the effect of improving the rust preventive property corresponding to the content cannot be obtained.

The component (2), which is an essential additive component constituting the rust preventive oil composition of the present invention, has a total base number by the perchloric acid method of JIS K 2501 of 20 to 500 mg KOH /
g, preferably 100 to 400 mg KOH / g, and one or more alkali metal and / or alkaline earth metal organic acid salts selected from phenates and salicylates.

Specific examples of the alkali metal include sodium and potassium, and specific examples of the alkaline earth metal include magnesium, calcium and barium.

The phenate as used herein means a so-called neutral (normal salt) phenate, basic phenate, carbonate overbased (superbasic) phenate and borate overbased (superbasic) phenate. Specifically, for example, an alkylphenol having 1 to 2 alkyl groups having 4 to 24 carbon atoms is treated with an alkali metal base (oxide or hydroxide of alkali metal) in the presence or absence of elemental sulfur. Substance) or an alkaline earth metal base (such as an oxide or hydroxide of an alkaline earth metal), which is a so-called neutral (normal salt) alkali metal and / or alkaline earth metal phenate; Neutral (normal salt)
So-called basic alkali metal and / or alkaline earth obtained by heating an alkali metal and / or alkaline earth metal phenate and an excess salt or base of alkali metal and / or alkaline earth metal in the presence of water. Metal-base basic phenate; a so-called carbonate overbased (super-basic) obtained by reacting a neutral alkali metal and / or alkaline earth metal phenate with an alkali metal or alkaline earth metal base in the presence of carbon dioxide gas. Basic) alkali metal and / or alkaline earth metal phenates; neutral alkali metal and / or alkaline earth metal phenates with alkali metal and / or alkaline earth metal bases and boric acid compounds such as boric acid or boric anhydride Or carbonate overbased (super basic) So-called borate overbased phenates produced by reacting potassium metal and / or alkaline earth metal phenates with boric acid compounds such as boric acid or boric anhydride; and mixtures thereof. Is mentioned.

The term "salicylate" as used herein means so-called neutral (normal salt) salicylate, basic salicylate, carbonate overbased (ultrabasic) salicylate and borate overbased (ultrabasic) salicylate. Specifically, for example, an alkyl salicylic acid having 1 to 2 alkyl groups having 4 to 24 carbon atoms is used in the presence or absence of elemental sulfur in the presence or absence of an alkali metal base (oxide of alkali metal or So-called neutral (normal salt) alkali metal and / or alkaline earth metal salicylates obtained by reacting with (e.g. hydroxide) or alkaline earth metal base (e.g. oxide or hydroxide of alkaline earth metal) ;
So-called basic, which is obtained by heating these neutral (normal salt) alkali metal and / or alkaline earth metal salicylates and excess alkali metal and / or alkaline earth metal salt or base in the presence of water. Alkali metal and / or alkaline earth metal salicylates; so-called carbonates obtained by reacting neutral alkali metal and / or alkaline earth metal salicylates with alkali metal or alkaline earth metal bases in the presence of carbon dioxide gas. Overbased (ultrabasic) alkali metal and / or alkaline earth metal salicylates; neutral alkali metal and / or alkaline earth metal salicylates with alkali metal and / or alkaline earth metal bases and boric acid or boric anhydride. Or reacted with boric acid compounds such as carbonates So-called borate overbased (superbasic) produced by reacting a basic (superbasic) alkali metal and / or alkaline earth metal salicylate with a boric acid compound such as boric acid or boric anhydride. Salicylates; and mixtures thereof.

In the present invention, among the above-mentioned alkali metal and / or alkaline earth metal organic acid salts as the component (2), a basic or organic acid salt is preferable because it is particularly excellent in rust preventive property, acid neutralizing property and degreasing property. Carbonate overbased (super basic)
Alkaline earth metal phenate or basic or carbonate overbased (super basic) alkaline earth metal salicylate,
Alternatively, a mixture thereof is preferably used, and a carbonate overbased (superbasic) alkaline earth metal phenate, a carbonate overbased (superbasic) alkaline earth metal salicylate,
Alternatively, a mixture of these is more preferably used.

In the present invention, it is important that the total base number of the component (2) by the perchloric acid method is within the above range, and when the total base number is less than this range or the total base number exceeds this range. Storage stability greatly deteriorates with
Each is not preferable.

In the present invention, the content of the component (2) is 0.1 to 20% by weight, preferably 0.5, based on the total amount of the composition.
10 to 10% by weight. When the component (2) is not used and when the content of the component (2) is less than 0.1% by weight, the storage stability of the composition is poor, while the content is 20% by weight.
If it exceeds, the storage stability becomes poor and the degreasing property remarkably deteriorates.

The component (3), which is an essential additive component constituting the rust preventive oil composition of the present invention, includes (a) oxidized wax and / or its derivative, (b) partial ester of polyhydric alcohol and ( c) At least one compound selected from lanolin fatty acid derivatives.

As used herein, (3) (a) Oxidized wax and / or derivative thereof refers to waxes such as paraffin wax, microcrystalline wax, petrolatum and polyolefin wax obtained by synthesis, which are obtained during the purification of petroleum fractions. Oxidized wax produced by oxidization of alkali metal; alkali metal salt, alkaline earth metal salt, alkali metal base (such as alkali metal oxide or hydroxide), alkaline earth metal base (alkaline earth metal) Oxide wax alkali metal salt or oxide wax alkaline earth metal salt in which some or all of the acidic groups of the wax have been neutralized by reacting metal oxides or hydroxides); 1 to
6 an aliphatic alcohol, specifically, for example, an oxidized wax esterified product obtained by reacting with methanol, ethanol, propanol, butanol, pentanol, hexanol or the like to esterify some or all of the acidic groups of the oxidized wax; These mixtures etc. are mentioned.

(3) (a) Oxidized wax of the present invention and / or
Alternatively, the saponification value and total acid value of the derivative are arbitrary,
Since the composition has excellent storage stability, oxidation stability, water displacement property and rust preventive property, the saponification value specified in JIS K 2503 is 50 to 80 mg KOH / g and the total acid value specified in JIS K 2501 is 2 to 2. Those having a property of 15 mgKOH / g are preferably used.

As the component (3) (a) of the present invention, an alkaline earth metal salt of an oxidized wax is preferably used, and a barium salt of oxidized paraffin is most preferably used, from the viewpoint of excellent rust preventive performance.

Further, (3) (b) the partial ester of a polyhydric alcohol is, for example, one or more polyhydric alcohols selected from glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitan. Partial esters of alcohol and fatty acids having 10 to 22 carbon atoms can be mentioned. The partial ester as used herein means an ester in which at least one or more hydroxyl groups in the polyhydric alcohol remain in the form of unesterified hydroxyl groups.

The fatty acid referred to herein may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Specifically, for example, decanoic acid (including all isomers), undecanoic acid (including all isomers),
Dodecanoic acid (including all isomers), tridecanoic acid (including all isomers), tetradecanoic acid (including all isomers), pentadecanoic acid (including all isomers), hexadecanoic acid (all isomers) Body), heptadecanoic acid (includes all isomers), octadecanoic acid (includes all isomers), nonadecanoic acid (includes all isomers), eicosanoic acid (includes all isomers), heneicosane Saturated fatty acids such as acids (including all isomers) and docosanoic acid (including all isomers); decenoic acid (including all isomers), undecenoic acid (including all isomers), dodecenoic acid ( (Including all isomers), tridecenoic acid (including all isomers), tetradecenoic acid (including all isomers),
Pentadecenoic acid (including all isomers), hexadecenoic acid (including all isomers), heptadecenoic acid (including all isomers), octadecenoic acid (including all isomers), nonadecenoic acid (all isomers) Body), eicosenoic acid (includes all isomers), heneicosenoic acid (includes all isomers), docosenoic acid (includes all isomers)
Unsaturated fatty acids such as; and mixtures thereof.

Specific examples of the component (3) (b) of the present invention include glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate,
Glycerin didodecanoate (glycerin dilaurate), glycerin diisolaurate, glycerin monotetradecanoate (glycerin monomyristate), glycerin monoisomyristate, glycerin ditetradecanoate (glycerin dimyristate), glycerin diiso Myristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin dihexadecanoate (glycerin dipalmitate), glycerin diisopalmitate, glycerin monooctadecanoate (glycerin mono) Stearate), glycerin monoisostearate, glycerin dioctadecanoate (glycerin distearate), glycerin diisostearate, glycerin monooctadeceno Over preparative (glycerin monooleate), glycerin monoisostearate oleate, glycerol di octadecenoate (glycerol dioleate), glycerin di iso oleate, trimethylolethane monododecanoate (trimethylolethane monolaurate),
Trimethylolethane monoisolaurate, trimethylolethane didodecanoate (trimethylolethane dilaurate), trimethylolethane diisolaurate, trimethylolethane monotetradecanoate (trimethylolethane monomyristate), trimethylolethane mono Isomyristate, trimethylolethaneditetradecanoate (trimethylolethanedimyristate), trimethylolethanediisomyristate,
Trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethane dihexadecanoate (trimethylolethane dipalmitate), trimethylolethane diisopalmitate, Trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane dioctadecanoate (trimethylolethane distearate), trimethylolethane diisostearate, Trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate, trimethylolethane dioctadecenoate (trimethylol Ruethane dioleate), trimethylolethane diisooleate, trimethylolpropane monododecanoate (trimethylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane didodecanoate (trimethylolpropane dilaurate) ), Trimethylolpropane diisolaurate, trimethylolpropane monotetradecanoate (trimethylolpropane monomyristate), trimethylolpropane monoisomyristate, trimethylolpropane ditetradecanoate (trimethylolpropane dimyristate) , Trimethylolpropane diisomyristate, trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylol B bread mono isobutyl palmitate, trimethylolpropane di hexa decanoate (trimethylol propane dipalmitate),
Trimethylolpropane diisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, trimethylolpropane dioctadecanoate (trimethylolpropane distearate), Trimethylolpropane diisostearate,
Trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate, trimethylolpropane dioctadecenoate (trimethylolpropane dioleate), trimethylolpropane diisooleate,
Pentaerythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol monoisolaurate, pentaerythritol didodecanoate (pentaerythritol dilaurate), pentaerythritol diisolaurate, pentaerythritol tridodecanoate (pentaerythritol trilaurate) Rate), pentaerythritol triisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol ditetradecanoate (pentaerythritol dimyristate), pentaerythritol diisolate Myristate, pentaerythritol tritetradecanoate (pentaerythritol trimyriate Tate), pentaerythritol triisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol dihexadecanoate (pentaerythritol dipalmitate), pentaerythritol di Isopalmitate, pentaerythritol trihexadecanoate (pentaerythritol tripalmitate), pentaerythritol triisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol Dioctadecanoate (pentaerythritol distearate), pentaerythritol diisosteare Pentaerythritol trioctadecanoate (pentaerythritol tristearate), pentaerythritol triisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol monoisooleate, pentaerythritol dioctaate Decenoate (pentaerythritol dioleate), pentaerythritol diisooleate, pentaerythritol trioctadecenoate (pentaerythritol trioleate), pentaerythritol triisooleate, sorbitan monododecanoate (sorbitan monolaurate) , Sorbitan monoisolaurate, sorbitan didodecanoate (sorbitan dilaurate), sorbitan diisolaurate, sorbi Tantric dodecanoate (sorbitan trilaurate), sorbitan triisolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan ditetradecanoate (sorbitan dimyristate),
Sorbitan diisomyristate, sorbitan tritetradecanoate (sorbitan trimyristate), sorbitan triisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan dihexadecanoate (Sorbitan dipalmitate), sorbitan diisopalmitate, sorbitan trihexadecanoate (sorbitan tripalmitate), sorbitan triisopalmitate, sorbitan monooctadecanoate (sorbitan monostearate), sorbitan monoisostearate , Sorbitan dioctadecanoate (sorbitan distearate), sorbitan diisostearate, sorbitan trioctadecanoate (sorbitan tristearate), sorbita Triisostearate, sorbitan monooctadecenoate (sorbitan monooleate), sorbitan monoisooleate, sorbitan dioctadecenoate (sorbitan dioleate), sorbitan diisooleate, sorbitan trioctadecenoate ( Sorbitan trioleate), sorbitan triisooleate, and mixtures thereof are preferably used, and especially monoesters such as glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, and glycerin monotetradecanoate. (Glycerin monomyristate), glycerin monoisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin monooctadecano (Glycerin monostearate), glycerin monoisostearate, glycerin monooctadecenoate (glycerin monooleate), glycerin monoisooleate, trimethylolethane monododecanoate (trimethylolethane monolaurate), Trimethylolethane monoisolaurate, trimethylolethane monotetradecanoate (trimethylolethane monomyristate),
Trimethylolethane monoisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethane monooctadecanoate (trimethylolethane monostearate), Trimethylolethane monoisostearate, trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate, trimethylolpropane monododecanoate (trimethylolpropane monolaurate), tri Methylolpropane monoisolaurate, trimethylolpropane monotetradecanoate (trimethylolpropane monomyristate), trimethylolpropane monoisomyliste DOO, trimethylolpropane monoallyl hexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisostearate palmitate, trimethylolpropane monoallyl octadecanoate (trimethylolpropane monostearate),
Trimethylolpropane monoisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate, pentaerythritol monododecanoate (pentaerythritol monolaurate),
Pentaerythritol monoisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate),
Pentaerythritol monoisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate),
Pentaerythritol monoisooleate, sorbitan monododecanoate (sorbitan monolaurate), sorbitan monoisolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan monohexadecanoate (Sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan monooctadecanoate (sorbitan monostearate), sorbitan monoisostearate, sorbitan monooctadecenoate (sorbitan monooleate), sorbitan monoisooleate , And mixtures thereof are more preferably used.

Examples of (3) (c) lanolin fatty acid derivative of the present invention include alkali metal salts, alkaline earth metal salts or esters of lanolin fatty acid. The alkali metal salt or alkaline earth metal salt of lanolin fatty acid is
Lanolin (wool fat) obtained by purifying waxy substances that adhere to sheep's hair is used as a base for oxides and hydroxides of alkali metals such as sodium and potassium and alkaline earth metals such as magnesium, calcium and barium. React with
A part or all of the fatty acid component contained in lanolin is a metal salt, and lanolin fatty acid ester is lanolin with polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitan. The fatty acid component contained in lanolin is partly or wholly esterified by reaction.

Although the saponification value and total acid value of the lanolin fatty acid derivative (3) (c) of the present invention are arbitrary, the composition is excellent in storage stability, oxidation stability, water displacement and rust resistance. According to JIS K 2503, saponification value 20-220
mgKOH / g and JIS K 2501 total acid value 1-15mg
Those having a property of K OH / g are preferably used.

In the present invention, the content of the component (3) is
0.1 to 20% by weight, preferably 1.
It is 0 to 10% by weight. When the component (3) is not used and when the content of the component (3) is less than 0.1% by weight, the rust preventive performance is poor, while when the content exceeds 20% by weight, the effect is saturated. In this state, the effect of improving the rust preventive property corresponding to the content cannot be obtained, which is not preferable.

In the present invention, the above-mentioned base oil is (1)
By combining the three types of additives (3) to (3) in specific amounts, excellent rust preventive performance is exhibited even in an acidic atmosphere, and the performance is maintained even after storage under high temperature and high humidity conditions. Although a rust preventive oil composition having excellent storage stability can be obtained, known additives used for ordinary rust preventive oils can be used together for the purpose of further enhancing the excellent performance.

Particularly preferred additives which can be used in combination are:
Phenol-based antioxidants are mentioned in terms of obtaining the effect of improving the stability of rust resistance. Specific examples of the phenolic antioxidant referred to herein include 2,6
-Di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2-methyl-6-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'- Methylenebis (2,6-di-tert-butylphenol), 4,4'-bis (2,6-di-tert-
Butylphenol), 4,4'-thiobis (6-tert-
Butyl-o-cresol), and mixtures thereof.

When a phenolic antioxidant is used in combination in the present invention, the content thereof is 0.1% based on the total amount of the composition.
It is desirable to add an amount of 1 to 1.0% by weight, preferably 0.4 to 0.6% by weight.

Further, other additives that can be used in the present invention include, for example, amine antioxidants such as phenyl-α-naphthylamine; basic or overbased sulfonates, phosphonates, naphthenates and the like. Detergents; Wetting agents such as diethylene glycol monoalkyl ethers; Metal deactivators such as benzotriazole and alkyl thiadiazoles; Acrylic polymers,
Film forming agents such as paraffin wax; water displacing agents such as fatty acid amine salts; zinc dialkyldithiophosphates, sulfurized fats and oils,
Extreme pressure agents such as phosphorus compounds; antifoaming agents such as silicone oil and fluorosilicone oil; crystalline substances such as paraffin wax, etc., and these may be used alone,
Moreover, you may use it in combination of 2 or more types. The content in the case of using these known additives in combination is arbitrary, but usually, an amount such that the total content of these known additives is 0.1 to 10% by weight based on the total amount of the composition is added. Is desirable.

The rust preventive oil composition according to the present invention is 40
℃ In 1~150mm ² / s, preferably not having a kinematic viscosity of 2 to 100 mm ² / s. The composition has a kinematic viscosity of 1 mm ² / s
If less than, the risk of ignition of the composition increases, while
When it exceeds 150 mm ² / s, the rust preventive oil film becomes extremely sticky and causes a problem in workability, which is not preferable.

In the present invention, the total base number of the entire composition is 1 to 30 mg KOH / g, preferably 1.5 to 15 mg.
It is important that it is in the range of KOH / g and the ratio of total base number (mgKOH / g) / total acid number (mgKOH / g) is in the range of 2 to 20, preferably 3 to 15. The total base number mentioned here means the total base number determined by the perchloric acid method specified in JIS K 2501, and the total acid number means the total acid number specified in JIS K 2501.

In the present invention, if the total base number of the composition as a whole is less than 1 mgKOH / g, or if the total base number exceeds 30 mgKOH / g, problems occur with the storage stability of the composition. . Also, the total base number of the entire composition
When the ratio of (mgKOH / g) / total acid value (mgKOH / g) is less than 2 and when this ratio exceeds 20, both are not preferable because problems occur in the storage stability of the composition.

The rust preventive oil composition of the present invention comprises iron, zinc,
It is excellent in rust preventive performance of various metals such as aluminum and alloys of these metals and other metals, and can be effectively used in various places where rust preventive properties of these metals are required.

[0041]

EXAMPLES Hereinafter, the contents of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these contents. (Example 1) A rust preventive oil composition according to the present invention was prepared with the composition shown in Table 1 using the following components. With respect to this composition, the following storage stability test, and performance evaluation immediately after formulation and after storage under the conditions of the following storage stability test were conducted by a salt spray test and an oil stain test, and the results are shown in Table 1. I also wrote it down.

(Examples 2 to 6) The rust preventive oil composition according to the present invention was prepared in the same manner as in Example 1 except that the following components were used and the composition shown in Table 1 was used. The results of performance evaluation performed in the same manner as in Example 1 are also shown in Table 1.

(Comparative Examples 1 to 3) For comparison, the components shown in Table 1 were used in the same manner as in Example 1 except that the component (2) which was an essential component of the present invention was contained. A composition not prepared was prepared. The results of performance evaluation performed in the same manner as in Example 1 are also shown in Table 1.

(Comparative Examples 4 to 5) The components shown in Table 1 were used in the same manner as in Example 1 except that the components (1) to (3), which are essential components of the present invention, were used. However, a composition having a total base number and a total base number / total acid number ratio outside the range of the present invention was prepared. The results of performance evaluation performed in the same manner as in Example 1 are also shown in Table 1.

Base oil A: paraffinic mineral oil solvent (kinematic viscosity 1.7 mm ² / s @
40 ° C) B: Paraffin mineral oil (kinematic viscosity 22.0 mm ² / s @ 40
℃)

(1) Component A: Neutral Ba petroleum sulfonate (total base number (perchloric acid method) 0.0 mg KOH / g) B: Neutral Ca petroleum sulfonate (total base number (perchloric acid method) 2.5 mg KOH / g)

(2) Component A: calcium carbonate overbased Ca phenate (total base number (perchloric acid method) 148 mgKOH / g) B: calcium carbonate overbased Ca phenate (total base number (perchloric acid method) 249 mg KOH / g) C: calcium carbonate overbased Ca salicylate (total base number (perchloric acid method) 166 mg KOH / g) D: calcium carbonate overbased Ca salicylate (total base number (perchloric acid method) 280 mg KOH / g)

(3) Component A: Oxidized wax Ba salt (saponification value 60 mgKOH / g, total acid value 4.0 mgKOH / g,
Ba content: 5.0 wt%) B: Oxidized wax Ba salt (saponification value: 75 mgKOH / g, total acid value: 12 mgKOH / g, B
a content 3.5% by weight) C: sorbitan monooleate D: lanolin fatty acid Ca salt (saponification value 30 mgKOH / g, total acid value 5.0 mgKOH / g,
Ca content 3.4% by weight)

Antioxidant A: 2,6-di-tert-butyl-p-cresol

[Storage stability test] Rust preventive oil composition 30
g in a 50 ml sample bottle and cover the opening to prevent direct entry of dew condensation water.
The composition was stored in a thermo-hygrostat adjusted to RH for 168 hours, and the presence or absence of precipitation of the composition after storage was visually judged. In addition, in the evaluation, those having no change in the composition were judged to be acceptable, and those in which turbidity and precipitation were generated were judged to be unacceptable.

[Salt Spray Test] According to the salt spray test specified in JIS K 2246 5.35, the test time until rust was generated was evaluated according to the following four grades. A: 48 hours or more B: 24 hours or more and less than 48 hours C: 12 hours or more and less than 24 hours D: Less than 12 hours

[Oil Stain Test] A rust preventive oil composition was applied to a steel sheet and stored at 60 ° C. and 95% humidity for 240 hours.
It was evaluated according to the grade. A: No oil stain B: Slight oil stain C: Light oil stain D: Strong oil stain in some areas E: Heavy oil stain

[0053]

[Table 1]

As is clear from the performance evaluation results in Table 1,
The rust preventive oil compositions of Examples 1 to 6 according to the present invention have excellent storage stability, and maintain excellent rust preventive performance before storage even after storage under high temperature and high humidity conditions.
On the other hand, when the component (2) is not contained (Comparative Example 1)
~ 3) and (1) to (3) components are used, but the total base number and the ratio of total base number / total acid number are outside the range of the present invention (Comparative Examples 4 and 5), Although there are some excellent rust preventive performances before storage, the performances are deteriorated after storage, and the storage stability is greatly inferior to the products of the present invention.

[0055]

The rust preventive oil composition of the present invention comprises a mineral oil or a synthetic oil as a base oil, and a basic alkali metal or alkaline earth metal organic acid selected from neutral metal sulfonates, phenates and salicylates. A specific amount of at least one selected from salts, oxidized waxes, partial esters of polyhydric alcohols and lanolin fatty acid derivatives,
In addition, the composition was prepared so that the kinematic viscosity, the total base number and the ratio of the total base number / the total acid number of the entire composition were in a specific range, and was very excellent even in an acidic atmosphere and in a thin film thickness. Since it has rust preventive performance and excellent storage stability that the performance is maintained even after storage under high temperature and high humidity conditions, it has high industrial utility value.

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Claims (1)

[Claims] 1. A mineral oil and / or a synthetic oil as a base oil, and on the basis of the total amount of the composition, (1) 0.1 to 20% by weight of a neutral alkali metal and / or alkaline earth metal sulfonate, (2) At least one alkali metal and / or alkaline earth metal organic acid salt having a total base number of 20 to 500 mg KOH / g selected from phenates and salicylates 0.1
To 20% by weight, and (3) at least 1 selected from the following (a) to (c):
0.1 to 20% by weight of a compound of the type, (a) an oxidized wax and / or its derivative, (b) a partial ester of a polyhydric alcohol, (c) a lanolin fatty acid derivative as an essential component, and at 40 ° C. of the composition. Has a kinematic viscosity of 1 to 150 mm ² / s and a total base number of 1 to 30 mg KO
A rust preventive oil composition having a ratio of H / g and total base number (mgKOH / g) / total acid number (mgKOH / g) of 2 to 20.