JP2003183864A - Anti-rust method - Google Patents

Abstract

(57) [Summary] [PROBLEMS] In a rust-preventing method involving the circulating use of rust-preventing oil, rust-preventing oil in a system is easily maintained while maintaining performance such as rust-preventing ability at a certain level or more. Provided is a rust-preventing method capable of reducing the number and amount of discarding. SOLUTION: In a rust-preventing method in which rust-preventing oil is circulated, (A) a kinematic viscosity at 40 ° C. of 10 to 2000 m is used as the rust-preventing oil to be initially filled (initial filling oil).
a mineral oil and / or synthetic oil having a m ² / s, and (B) a sulfonate of an alkali metal, an alkaline earth metal or an amine derivative, and having a kinematic viscosity at 40 ° C. of 2 to 10
00 mm ² / s or an apparent viscosity at 25 ° C. of 3 to
The initial filling oil of 1000 mPa · s is used, and the kinematic viscosity at 40 ° C. is 1.5 to 40 times the kinematic viscosity at 40 ° C. of the initial filling oil as a rust preventive oil (supplement oil) for replenishment, or The problem was solved by using a replenishing oil having an apparent viscosity at 25 ° C of 1.5 to 40 times the apparent viscosity of the initial filling oil at 25 ° C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust preventive method for precision parts and metallic materials such as steel plates, and more particularly to a rust preventive method involving circulating use of rust preventive oil.

[0002]

2. Description of the Related Art When a metal material is subjected to a rust preventive treatment using a rust preventive oil, the rust preventive oil is usually circulated and used because the work is efficiently performed as a line work. For example, the rust preventive oil filled in the tank is delivered and sprayed on the metal material, and the rust preventive oil that has flowed down is collected again in the tank.

When the rust preventive treatment accompanied by such circulation of the rust preventive oil is carried out, the rust preventive oil adheres to the metal material which is sequentially passed and is lost, and thus the circulation usually in the tank. The rust preventive oil in the system is reduced. In order to compensate for this decrease, conventionally, the same rust preventive oil as the rust preventive oil initially filled in the circulatory system has been added to the circulatory system in a reduced amount. However, if the rust preventive oil is used for a long time in the circulation system, kerosene used in the cleaning process, which is the pre-process of rust preventive, mixes with the rust preventive oil, so the rust preventive oil has a low viscosity. To do. The viscosity of the rust preventive oil is adjusted to be most suitable for the rust preventive system in consideration of the rust preventive property and the handling property. Therefore, lowering the viscosity of the rust preventive oil may cause a system malfunction such as a decrease in the rust preventive property. For this reason, first fill the rust preventive oil, and after a certain period of time has passed since the start of the rust preventive work, discard part or all of the rust preventive oil in the system, and replenish and replace the same rust preventive oil. Is being done.

Further, in order to maintain the performance of the rust preventive oil, it is preferable to perform the disposal process as frequently as possible in order to eliminate the problems caused by the low viscosity of the rust preventive oil as much as possible. However, disposal and replacement of rust preventive oil is costly, and the environmental load associated with waste disposal is large. Therefore, there is a demand for a rust preventive method that can maintain the performance of the rust preventive oil above a certain level and reduce the number and amount of replacement and disposal of the rust preventive oil.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a rust preventive method involving the cyclic use of rust preventive oil, while easily maintaining the rust preventive oil's performance such as rust preventive ability above a certain level. An object of the present invention is to provide a rust preventive method capable of reducing the number of times and the amount of waste rust preventive oil in the system.

[0006]

As a result of various studies to solve the above problems, the present inventors have used a specific rust preventive oil as the rust preventive oil for initial filling and specified it as a rust preventive oil for replenishment. By using a rust preventive oil having a viscosity, it has been found that the rust preventive ability can be maintained while maintaining the viscosity of the rust preventive oil in a certain range, and the number of times and the amount of the rust preventive oil in the system can be discarded can be reduced. It has been completed.

That is, the present invention relates to a rust preventive method for circulating and using rust preventive oil, which comprises a step of bringing rust preventive oil into contact with a metal material and a step of replenishing rust preventive oil. As oil (initial filling oil),
(A) Kinematic viscosity at 40 ° C. is 10 to 2000 mm ² /
5 to 95% by mass of mineral oil and / or synthetic oil based on the total amount of the initial filling oil and (B) 1 to 10% by mass of the sulfonate of an alkali metal, an alkaline earth metal or an amine derivative based on the total amount of the initial filling oil. %, And an initial filling oil having a kinematic viscosity at 40 ° C. of ² to 1000 mm ² / s is used as a rust preventive oil (replenishing oil) for replenishment, and the initial filling oil has a kinematic viscosity at 40 ° C. Kinematic viscosity at 40 ° C of 1.5-4
It relates to a method for preventing rust, which is characterized by using 0 times as much makeup oil.

The present invention also provides a rust preventive method in which rust preventive oil is circulated and used, including a step of bringing rust preventive oil into contact with a metal material and a step of replenishing rust preventive oil,
As rust preventive oil to be initially filled (initial filling oil),
(A) Kinematic viscosity at 40 ° C. is 10 to 2000 mm ² /
5 to 95% by mass of mineral oil and / or synthetic oil based on the total amount of the initial filling oil and (B) 1 to 10% by mass of the sulfonate of an alkali metal, an alkaline earth metal or an amine derivative based on the total amount of the initial filling oil. %, And using an initial filling oil having an apparent viscosity at 25 ° C. of 3 to 1000 mPa · s, as a rust preventive oil (replenishing oil) for replenishment, 25 ° C.
The rust preventive method is characterized in that a supplemental oil having an apparent viscosity of 1.5 to 40 times the apparent viscosity at 25 ° C. of the initial filling oil is used.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The anticorrosion method of the present invention can be applied to anticorrosion of various metallic materials. Examples of the metal material include various hot-rolled steel sheets for automobile bodies, home appliances, and construction, cold-rolled steel sheets, high-tensile strength steel sheets, plated steel sheets (galvanized steel sheets, galvannealed steel sheets, etc.) , Stainless steel plates, ball screw parts, bearings, steel balls, precision parts such as guide rails, sintered metal parts, aluminum alloys, magnesium alloys, copper alloys, titanium alloys, and many other metallic materials.

The rust preventive method of the present invention includes a step of bringing rust preventive oil into contact with a metallic material while circulating the rust preventive oil. The rust preventive oil is brought into contact with the metal material by, for example, spraying, dropping, dipping, brush coating, electrostatic coating, or the like, and the rust preventive oil is applied to the surface of the metal material. In addition, it is also preferable to provide a drain cutting process using a centrifuge or a drain cutting process after leaving for a long time after the excess rust preventive oil is applied.

By collecting the rust preventive oil brought into contact with the metal material and using it again, it is possible to use the rust preventive oil while circulating it. When circulating the rust preventive oil, it is preferable to remove foreign substances mixed in the circulation system. For example, on the way of the circulation path of rust preventive oil,
Preferably, a filter can be provided to remove foreign matter immediately before the rust preventive oil is jetted to bring it into contact with the metallic material. Further, a magnet may be provided at the bottom of the tank that stores the rust preventive oil, and foreign matter such as abrasion powder can be adsorbed and removed by magnetic force.

The rust preventive method of the present invention includes the step of supplying rust preventive oil to the circulation system. The replenishment of the rust preventive oil may be carried out together with the decrease of the amount of the rust preventive oil in the circulation system or the decrease of the viscosity of the rust preventive oil in the circulation system. When the amount of rust preventive oil is reduced and the amount of rust preventive oil in the circulation system is reduced by more than a predetermined amount from the amount initially filled in the circulation system, This can be done by replenishing so that the amount is the same as the amount initially filled. The predetermined amount can be set as appropriate, but 5 to 30% by volume of the initial filling amount
Values between and are preferred.

In the operation of replenishing the rust preventive oil, in order to maintain the rust preventive ability of the rust preventive oil in the circulation system at a higher level, a part of the rust preventive oil in the circulation system is recirculated if necessary. You may also perform the operation of discharging outside. For example, 1 to 6 of rust preventive oil in the circulation system prior to the operation of replenishment
It can be carried out by discharging 5% by volume to the outside of the circulation system and then performing a replenishment operation to restore the amount of rust preventive oil in the circulation system to the same amount as the initial filling amount.

As the rust preventive oil used for the replenishment, not only the rust preventive oil for replenishment but also the initial filling oil may be used together. In particular, when 1 to 65% by volume of the rust preventive oil in the circulation system is discharged to the outside of the circulation system before the replenishment operation, and it is preferable to use the initial filling oil together when the replenishment operation is performed thereafter. is there.

In the present invention, the initial filling of the rust preventive oil means that the whole amount of the rust preventive oil in the circulation system is newly charged or a part of the rust preventive oil already filled is discharged to the outside of the circulation system. After discharging, it means filling new rust preventive oil so that 70% by volume or more of the rust preventive oil in the circulation system is occupied by the new rust preventive oil.

In the rust preventive method of the present invention, a specific rust preventive oil (initial charge oil) is used as the rust preventive oil used for the initial filling.

The initial filling oil has a kinematic viscosity at 40 ° C. of 10 to 10.
It contains mineral and / or synthetic oils of 2000 mm ² / s. As the mineral oil, for example, with respect to a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and vacuum distillation, solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing,
Examples thereof include paraffin-based or naphthene-based mineral oils obtained by applying one or two or more types of refining means such as hydrorefining, sulfuric acid washing, and clay treatment as appropriate. Examples of the synthetic oil include ethylene-propylene copolymer, polybutene (polymer of a mixture of 1-butene, 2-butene and isobutene), 1-octene oligomer, 1
Examples thereof include decene oligomers, 1-dodecene oligomers, polyolefins such as hydrides thereof, and alkylbenzenes.

The content ratio of the mineral oil and / or the synthetic oil in the initial filling oil is 5% by mass or more based on the total amount of the initial filling oil,
It is preferably 10% by mass or more, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
It is not more than mass%.

The initial filling oil of the present invention may contain a hydrocarbon light oil having a kinematic viscosity at 40 ° C. of less than 10 mm ² / s. Examples of the hydrocarbon light oil include the same kind as the mineral oil and / or the synthetic oil.

The hydrocarbon-based light oil preferably has an aromatic content of 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. More preferable. When the content of the aromatic component satisfies the above condition, the compatibility with the organic material tends to be further enhanced. The aromatic content here means
Fluorescent indicator adsorption method (FIA) of "Petroleum products-hydrocarbon type test method" described in JIS K 2536
Method) ”, which is a value [mass%] measured in accordance with Further, in consideration of the working environment and the global environment, it is desirable that the aromatic content is 9 mass% or less, preferably 5 mass% or less.

When the initial filling oil contains the above hydrocarbon light oil, the content ratio is not particularly limited, but is preferably 10% by mass or more, and more preferably 20% by mass or more based on the total amount of the initial filling oil. More preferably, it is 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

Further, in the present invention, the initial filling oil contains a sulfonate of an alkali metal, an alkaline earth metal or an amine derivative.

Examples of the alkali metal constituting the sulfonate include sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium and barium. Of these, sodium, potassium and calcium are preferable.

Examples of the amine include monoamine, polyamine, alkanolamine and the like. Examples of the monoamine include amines having 1 to 3 hydrocarbon groups. Specific examples of the hydrocarbon group mentioned here include an alkyl group, an alkenyl group, an aryl group, and a cycloalkyl group. The monoamine also includes monoamines derived from fats and oils such as beef tallow amine. Examples of the polyamine include alkylene polyamine, N-alkyl alkylene polyamine, N-alkenyl alkylene polyamine and the like. The polyamine also includes polyamines derived from fats and oils such as beef tallow polyamine. Examples of the alkanolamine include alkanol groups of 1 to 3
And amines having 0 to 2 hydrocarbon groups.

Among the above-mentioned amines, monoamines are preferable from the viewpoint of stain resistance, and among them, alkylamines, monoamines having an alkyl group and an alkenyl group, monoamines having an alkyl group and a cycloalkyl group, cycloalkylamines, And alkylcycloalkylamines are more preferred. From the viewpoint of stain resistance, 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.

On the other hand, as the sulfonic acid used in the sulfonate, a conventionally known one prepared by a conventional method can be used. Specifically, sulfonated alkyl aromatic compounds of lubricating oil fraction of mineral oil, petroleum sulfonic acid such as so-called mahogany acid produced as a by-product during the production of white oil, or an alkylbenzene production plant as a raw material for detergents, etc. Synthetic sulfone such as sulfonated alkylbenzene having a linear or branched alkyl group, obtained by alkylating a olefin with benzene, and sulfonated alkylnaphthalene such as dinonylnaphthalene. Acid, etc. are mentioned. The molecular weight of these sulfonic acids is not particularly limited, but those having a molecular weight of 100 to 1500, and more preferably 200 to 700 are used.

Among the above-mentioned sulfonic acids, 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 linear alkyl groups or A branched alkyl group having one side chain methyl group,
And at least 1 selected from the group consisting of dialkylbenzenesulfonic acid having two alkyl groups having a total carbon number of 14 to 30; and monoalkylbenzenesulfonic acid having an alkyl bonded to a benzene ring having 15 or more carbon atoms.
It is preferred to use seeds.

As described above, the dialkylnaphthalenesulfonic acid preferably used in the present invention is one in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30. If the total number of carbon atoms of the two alkyl groups is less than 14, the anti-emulsifying property tends to be insufficient, while if it exceeds 30, the storage stability of the rust preventive oil obtained tends to decrease. The two alkyl groups may be linear or branched. Further, if the total number of carbon atoms of the two alkyl groups is 14 to 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 to 18, respectively.

The dialkylbenzenesulfonic acid preferably used in the present invention is, as described above, a branched alkyl group in which each of the two alkyl groups bonded to the benzene ring has one linear alkyl group or one side chain methyl group. It is an alkyl group, and the total number of carbon atoms of the two alkyl groups is 14 to 30. In the case of monoalkylbenzene sulfonic acid, it can be suitably used as long as the alkyl group has 15 or more carbon atoms as described later. However, when a monoalkylbenzene sulfonic acid having an alkyl group having less than 15 carbon atoms is used, a rust preventive oil can be used. The storage stability of is likely to decrease.

Also, when an alkylbenzene sulfonic acid having 3 or more alkyl groups is used, the storage stability of the rust preventive oil tends to decrease. Further, the alkyl group bonded to the benzene ring of the dialkylbenzenesulfonic acid has a branched structure other than a side chain methyl group (for example, a branched chain alkyl group having a side chain ethyl group) or two or more. A branched chain alkyl group having a branched structure (for example, a branched chain alkyl group derived from an oligomer of propylene) may adversely affect the human body or the ecosystem, and the rust preventive property is unsatisfactory. Tends to be sufficient.

Furthermore, when the total number of carbon atoms of the two alkyl groups bonded to the benzene ring of the dialkylbenzene sulfonic acid is less than 14, the demulsifying property tends to be lowered, while when it exceeds 30, the rust preventive oil of the rust preventive oil tends to be deteriorated. Storage stability tends to decrease. The total number of carbon atoms of the two alkyl groups bonded to the benzene ring is not particularly limited as long as the total number of carbon atoms of each alkyl group is 14 to 30, but the number of carbon atoms of each alkyl group is 6 to 18, respectively. Is preferred.

Further, the monoalkylbenzenesulfonic acid preferably used in the present invention is one in which one alkyl group bonded to the benzene ring has 15 or more carbon atoms, as described above. If the alkyl group bonded to the benzene ring has less than 15 carbon atoms, the storage stability of the resulting rust preventive oil tends to be low. The alkyl group bonded to the benzene ring may be linear or branched as long as it has 15 or more carbon atoms.

Specific examples of the sulfonate obtained using the above raw materials include the following. That is, alkali metal bases (alkali metal oxides and hydroxides), alkaline earth metal bases (alkaline earth metal oxides and hydroxides) or amines (ammonia, alkylamines, alkanolamines, etc.). ) With a sulfonic acid; a neutral (normal salt) sulfonate; a neutral (normal salt) sulfonate as defined above, and an excess alkali metal base, alkaline earth metal base or amine. Basic sulfonic acid salt obtained by heating in the presence of water; the neutral (orthosalt) sulfonic acid salt described above in the presence of carbon dioxide gas with an alkali metal base, an alkaline earth metal base or an amine. A carbonate overbased (superbasic) sulfonate obtained by reacting the above neutral (orthosalt) sulfonate with an alkali metal base, an alkaline earth metal base or an amine. And obtained by a reaction with a boric acid compound such as boric acid or boric anhydride, or a reaction between the above-mentioned carbonate overbased (superbasic) sulfonate and a boric acid compound such as boric acid or boric anhydride. Examples include borate overbased (superbasic) sulfonates, mixtures thereof, and the like.

In the case of producing the above neutral (normal salt) sulfonate, the same alkali metal, alkaline earth metal or amine chloride as the desired sulfonate is added as a reaction accelerator, or The same alkali metal alkaline earth metal or amine chloride as the desired sulfonate after preparing a neutral (orthosalt) sulfonate of an alkali metal, alkaline earth metal or amine different from the desired sulfonate It is also possible to obtain the desired sulfonate by adding and adding to carry out an exchange reaction. However, since chloride ions tend to remain in the sulfonate obtained by such a method, in the present invention, the sulfonate obtained by such a method is not used, or the sulfonate obtained is not used. It is preferable to perform sufficient washing treatment such as washing with water. Specifically, the chlorine concentration in the sulfonate is preferably 200 mass ppm or less, more preferably 100 mass ppm or less,
More preferably 50 mass ppm or less, 25
Most preferably, it is not more than ppm by mass.

The content of the sulfonate in the initial filling oil of the present invention is preferably 1 to 10% by mass based on the total amount of the initial filling oil. When the content of the sulfonate according to the present invention is less than 1% by mass based on the total amount of the initial filling oil, the rust preventive property tends to be insufficient. For the same reason, the content of the sulfonate is more preferably 2% by mass or more, further preferably 4% by mass or more, based on the total amount of the initial filling oil. On the other hand, when the content of the sulfonate in the initially filled oil of the present invention exceeds 10% by mass, the effect of improving the rust preventive property commensurate with the content tends to be not observed. For the same reason, the content of the sulfonate according to the present invention is more preferably 9% by mass or less, and further preferably 8% by mass or less, based on the total amount of the initial filling oil.

In the present invention, the content of the sulfonate is the content of the sulfonate in the case of the neutral (normal salt) sulfonate, and the content of the sulfonate is the basic sulfonate. , Carbonate overbased (superbasic) sulfonates and borate overbased (superbasic) sulfonates, the total amount of sulfonate is added, including the basic salt in excess. Is.

In the present invention, it is possible to use a commercially available solution in which the above sulfonate is dissolved in a carrier oil in an amount of about 20 to 60% by mass. In the case of using such a mode, a solution is weighed and blended in such an amount that the net sulfonate has a desired blending amount (for example, in the case of a 50 mass% solution, twice the desired blending amount). By doing so, the desired blending amount can be adjusted.

In addition, the initial filling oil may further contain other additives. Specifically, paraffin wax and petrolatum, which have a remarkable effect of improving anti-corrosion properties in an acidic atmosphere; sulfurized fats and oils, sulfurized esters, long-chain alkylzinc dithiophosphates and partial esters, which have a remarkable effect of improving press moldability or lubricity. , Phosphates such as tricresyl phosphate, fats and oils such as lard,
Fatty acids, higher alcohols, calcium carbonate, potassium borate; phenolic or amine antioxidants for improving antioxidant performance; corrosion inhibitors for improving corrosion protection performance (benzotriazole or its derivatives, thiadiazole, benzo Thiazole, etc.); wetting agent such as diethylene glycol monoalkyl ether; film forming agent such as acrylic polymer, paraffin wax, microwax, slack wax, polyolefin wax; rust preventive additive other than the above-mentioned specific sulfonate; methylsilicone, fluoro Antifoaming agents such as silicones and polyacrylates; water and surfactants for removing water-soluble spoilage factors; or mixtures thereof and the like can be included.

Specific examples of the rust preventive additives other than the specific sulfonates include stearic acid, monocarboxylic acids represented by coconut oil fatty acid, etc., alkyl or alkenyl succinic acids (including anhydrides), or Derivatives thereof, dicarboxylic acids represented by dimers of unsaturated fatty acids such as oleic acid, hydroxy fatty acids, mercapto fatty acids, other polar group-containing carboxylic acids represented by sarcosine derivatives, carboxylic acids such as waxes; Metal salts of carboxylic acids such as fatty acid, naphthenic acid, resin acid, lanolin fatty acid, alkenyl succinic acid, amino acid derivative, and oxidized wax (sodium salt, potassium salt, calcium salt, barium salt, magnesium salt, aluminum salt, zinc salt, lead) Salt) and amine salt (monoamine salt, tallow amine salt, polyamine salt, alkanol salt) Carboxylic acid salts represented by carboxylic acid salts, etc.); esters represented by esters (including partial esters) of polyhydric alcohols such as glycerin, pentaerythritol, sorbitol and sucrose with carboxylic acids such as lauric acid and oleic acid. Kinds; higher fatty alcohols,
Alcohols typified by ethylene oxide adducts of alkylphenols; amines typified by dicyclohexylamine, morpholine, alkanolamines; typified by phosphoric acid monoesters, phosphodiesters, phosphite esters, and amine salts thereof (Sub) phosphoric acid derivatives; boron compounds and the like.

When the initial filling oil contains these additives, the content thereof is arbitrary, but normally, the content is such that the total content of these additives is 10% by mass or less based on the total amount of the initial filling oil. It is desirable to include.

The viscosity of the initial filling oil in the present invention is 40.
Kinematic viscosity at ℃ is ² ~ 1000mm ² / s, 3mm ²
/ S or more is preferable, and 4 mm ² / s or more is more preferable. Further, it is preferably 500 mm ² / s or less, more preferably 300 mm ² / s or less, and further preferably 100 mm ² / s or less.

Alternatively, the viscosity of the initial filling oil in the present invention is such that the apparent viscosity at 25 ° C. is 3 to 1000 mPa · s, preferably 3 mPa · s or more, and 4 mP.
It is more preferably a · s or more, further preferably 5 mPa · s or more. Also, 500 mPa
It is preferably s or less, more preferably 300 mPa · s or less, and further preferably 100 mPa · s or less.

Kinematic viscosity of the initial filling oil at 40 ° C. or 25
If the apparent viscosity at 0 ° C. is lower than the lower limit, the rust preventive property may be insufficient, and if it is higher than the upper limit, handleability may be poor. The apparent viscosity is JIS K
71117-1 "Plastic-Liquid, Emulsion or Dispersion Resin-Measuring Method of Apparent Viscosity by Brookfield Rotational Viscometer", the apparent viscosity measured by Brookfield type rotational viscometer of B type was measured. Show.

In the rust preventive method of the present invention, a specific replenishment rust preventive oil (supplementary oil) is used as the rust preventive oil replenished to the circulation system.

The supplementary oil according to the present invention is 4
The kinematic viscosity at 0 ° C is 1.
5 to 40 times, or the apparent viscosity at 25 ° C. as a replenishing oil is 1.5 to 4 that of the initial filling oil at 25 ° C.
It is 0 times. If the kinematic viscosity of the replenishing oil at 40 ° C is less than 1.5 times the kinematic viscosity of the initial filling oil at 40 ° C, or if the apparent viscosity of the replenishing oil at 25 ° C is the apparent viscosity of the initial filling oil at 25 ° C. When the viscosity is less than 1.5 times, the viscosity of the rust preventive oil in the circulation system is not recovered even when it is used as a replenishing oil, and as a result, the rust preventive property is deteriorated. For the same reason, it is preferable that each viscosity is twice or more. On the other hand, when it exceeds 40 times, the viscosity becomes too high and the handleability may deteriorate. For the same reason, it is preferably 25 times or less,
It is more preferable that the amount is not more than twice.

As the base oil of the replenishing oil, mineral oil, synthetic oil, hydrocarbon type light oil and the like used for the initial filling oil can be used.

As the additive to be added to the replenishing oil, those mentioned as the additives to be added to the initial filling oil can be used. The amount of addition is also the same as in the case of the initial filling oil. Among them, it is preferable to contain the sulfonate which is the component (B) of the initial filling oil. The content of the sulfonate in the makeup oil is optional, but the content in the initial filling oil should be 0.7 to 1.5 times the total amount of the rust preventive oil composition. Is preferred.

Further, paraffin wax having a remarkable effect of improving the anticorrosion property in the initial filling oil by exposure to an acidic atmosphere; sulfurized fats and oils, a sulfurized ester, a long-chain alkylzinc dithiophosphate, which has a remarkable effect of improving the press moldability or the lubricity, Contains partial esters, phosphates such as tricresyl phosphate, fats and oils such as lard, fatty acids, higher alcohols, calcium carbonate, potassium borate; water and surfactants for removing water-soluble spoilage factors In this case, it is preferable that these are also blended in the makeup oil. In addition, the content is 1.1 to 10 based on the total amount of the rust preventive oil composition with respect to the content in the initial filling oil.
It is preferable that the content is 1.5 times,
It is more preferably 1.5 to 4 times, and even more preferably 2 to 3.5 times.

The content of barium, zinc, chlorine and lead in the initial filling oil and the replenishing oil in the present invention is preferably 1000 mass ppm or less in terms of element based on the total amount of the rust preventive oil composition, and more preferably Preferably 50
0 mass ppm or less, more preferably 100 mass ppm
Or less, more preferably 50 mass ppm or less, further preferably 10 mass ppm or less, most preferably 5 mass p
It is pm or less. If the content of even one of these elements exceeds 1000 mass ppm, the safety to the environment such as the human body or the ecosystem tends to be insufficient.

The content of elements in the present invention means
The value measured by the following method. That is, the barium, zinc and lead contents are ASTM D 5185-95 "
Standard Test Method for Determination of Additive
Elements, Wear Metals, and Contaminants in Used L
ubricating Oils and Determination of Selected Elem
ents in Base Oils by Inductively Coupled Plasma At
omic Emission Spectrometry (ICP-AES) "; chlorine content is" IP PRPOSED METHOD AK / 81 Determination of ch
lorine-Microcoulometery oxidative method "means the content [mass ppm] based on the total amount of the rust preventive oil composition measured according to each method. The detection limit of each element in the above measurement method is usually 1 mass ppm. Is.

Further, in the initial filling oil and the makeup oil of the present invention, the content of the compound having a group represented by the following general formula (1) is 100 based on the total amount of the rust preventive oil composition.
It is preferably 0 mass ppm or less, more preferably 500 mass ppm or less, further preferably 100 mass ppm or less, further preferably 50 mass ppm or less, further preferably 10 mass ppm or less, most preferably 5 mass ppm or less.
The mass is less than or equal to ppm. When the content of the compound having a group represented by the general formula (1) exceeds 1000 mass ppm,
There is a tendency for the safety to the environment such as the human body and ecosystem to become insufficient.

[0052]

[Chemical 1]

In the general formula (1), R ¹ represents an alkyl group having 1 to 24 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 5, and n represents It represents an integer of 1 to 6.

Examples of the compound having a group represented by the general formula (1) include compounds represented by the following general formulas (2) to (4).

[0055]

[Chemical 2]

In the general formulas (2) to (4), A represents a group represented by the general formula (1), R ³ represents a hydrocarbon group having 1 to 24 carbon atoms or an acyl group having 1 to 24 carbon atoms. Represents

Elements such as barium, zinc and chlorine,
Alternatively, when the compound having a group represented by the above general formula (1) is contained in a raw material such as a sulfonate or a base oil used in the present invention, or is mixed in a rust preventive oil manufacturing process. In addition, the above elements and compounds can be removed by purifying the raw material or rust preventive oil by a conventional method. In addition, in the manufacturing process of the base oil and additives used in the present invention, do not share the manufacturing equipment with the manufacturing process of other base oils and additives, if shared, perform sufficient washing, As described in the method for producing sulfonates, use of sulfonates with a low concentration of chlorides, etc. prevents the inclusion of these elements and compounds in rust preventive oil. can do.

[0058]

EXAMPLES The contents of the present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 and Comparative Examples 1 to 5 Various rust preventive oils as initial filling oil and makeup oil were prepared according to the compositions shown in Table 1 (Compositions 1 to 8). Each component used is shown below. a) Mineral oil 1: Kinematic viscosity at 40 ° C .: 6.5 mm ² / s, aromatic content: 13% b) Mineral oil 2: Kinematic viscosity at 40 ° C .: 22 mm ² / s c) Mineral oil 3: Kinematic viscosity at 40 ° C .: 100 mm ² / s d) Mineral oil 4: Kinematic viscosity at 40 ° C .: 400 mm ² / s e) Mineral oil 5: Kinematic viscosity at 40 ° C .: 2 mm ² / s, aromatic content: 0.5% f) Mineral oil 6: 40 ° C. Kinematic viscosity: 1 mm ² / s, aromatic content: 7.5% g) Mineral oil 7: Kinematic viscosity at 40 ° C .: 1.5 mm ² / s, aromatic content: 0.3% h) Additive 1: Di Nonylnaphthalene Ca sulfonate solution (carrier oil 50%, total base number: 1 mgKOH /
g) i) Additive 2: Alkylbenzene Ba sulfonate solution (carrier oil 50%, total base number: 35 mg KOH /
g) j) Additive 3: Oxidized paraffin Ca salt (total acid value: 5 mg)
KOH / g, total base number: 16 mg KOH / g, saponification number: 80 mg KOH / g) k) Additive 4: Ca salt of lanolin fatty acid (total acid number: 2.
5 mgKOH / g, total base number: 11 mgKOH / g, saponification number: 120 mgKOH / g) 1) Additive 5: di-tert-butyl-p-cresol m) Additive 6: petrolatum

[0060]

[Table 1]

When each composition was used as an initial filling oil and a makeup oil, a test was conducted to examine how the rust preventive property changes after a certain period of time. That is, in a rust preventive oil application device that uses 1000 liters of rust preventive oil in the circulation system, the carry-out amount of rust preventive oil is 1 per day.
00L, kerosene (Kinematic viscosity at 40 ℃ 1.4mm ²
/ S) is 20L per day, and assuming that the rust preventive oil is replenished when the capacity of the rust preventive oil in the circulation system decreases by 20%, the rust preventive oil in the circulation system after 30 days The estimated evaluation oil was prepared. 1) Evaluation oil 1: 100% by volume of initial filling oil 2) Evaluation oil 2: 4% by volume of initial filling oil, 75% by volume of makeup oil, 21% by volume of kerosene

Next, with respect to the evaluation oils 1 and 2, the wet rust preventive property and the exposure rust preventive property were evaluated by the following methods. The results are shown in Table 2. 1) Wet rust resistance Commercially available cold rolled steel plate equivalent to SPCE-SD 60 x 80 mm
It was cut into a test piece. The sample oil was applied to this test piece using an air sprayer so as to have a concentration of 20 g / m ² . Thereafter, the test piece was held vertically for 24 hours. Other test conditions were performed by the wet test method defined in JIS K2246. Rank C is the case where rust is generated within 3 days after application, Rank B is the case where rust is generated within 4 to 9 days after application, Rank A is the case where rust is generated within 10 days to 29 days after application. The case where no rust was generated for the next 30 days was evaluated as rank S.

2) Exposure to anticorrosive properties The same test pieces as those used in the wet anticorrosion properties test were coated with the sample oil in the same manner as in the wet anticorrosion properties test, and stored in a hundred-leaf box installed outdoors. If rust is generated within 3 days after application, rank D is given; if rust is generated 4 to 9 days after application, rank C; if rust is produced 10 to 19 days after application, rank B is applied. The case where rust was generated for 20 days to 29 days was evaluated as rank A, and the case where rust was not generated for 30 days after application was evaluated as rank S.

[0064]

[Table 2]

As is clear from the results shown in Table 2, the anticorrosion property of the present invention was equivalent to that of the initial filling oil even after 30 days by using the anticorrosion method of the present invention.

As described above, by using the specific rust preventive oil as the rust preventive oil for the initial filling and the rust preventive oil having the specific viscosity as the replenishment rust preventive oil, it is possible to circulate it for a long time. Since the viscosity of the rust preventive oil can be maintained within a certain range and the rust preventive performance can be maintained, it is possible to reduce the number of times and the amount of the rust preventive oil to be discarded.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C10N 10:02 C10N 10:02 10:04 10:04 20:02 20:02 30:12 30: 12 (72) Inventor Yukio Matsuzaki 8th Chidori-cho, Naka-ku, Yokohama, Kanagawa F-term in Sanritsu Hishiishi Co., Ltd. (reference) 4H104 BG06 DA02 EB10 FA01 FA02 LA06 4K062 AA01 AA03 BA08 BB01 BB05 BB06 BB12 BB18 BB21 BC02 BC06 BC16 FA11 FA12 GA02 GA04 GA05

Claims (3)

[Claims] 1. A rust preventive oil that is initially filled in a rust preventive method that circulates and uses rust preventive oil including a step of bringing rust preventive oil into contact with a metal material and a step of replenishing rust preventive oil. As the oil), (A) a mineral oil and / or a synthetic oil having a kinematic viscosity at 40 ° C. of 10 to 2000 mm ² / s in an amount of 5 to 95% by mass based on the total amount of the initial filling oil, and (B) an alkali metal or an alkaline earth metal. Alternatively, the sulfonate of the amine derivative is 1 to 1 based on the total amount of the initial filling oil.
It contains 0 mass% and has a kinematic viscosity at 40 ° C. of 2 to 100.
Using an initial filling oil of 0 mm ² / s, as a rust preventive oil (replenishing oil) for replenishment, the kinematic viscosity at 40 ° C. is 1.5 to 40 times the kinematic viscosity of the initial filling oil at 40 ° C. A rust preventive method characterized by using a certain make-up oil. 2. In a rust preventive method of circulating and using rust preventive oil, including a step of contacting rust preventive oil with a metal material and a step of replenishing rust preventive oil As the oil), (A) a mineral oil and / or a synthetic oil having a kinematic viscosity at 40 ° C. of 10 to 2000 mm ² / s in an amount of 5 to 95% by mass based on the total amount of the initial filling oil, and (B) an alkali metal or an alkaline earth metal. Alternatively, the sulfonate of the amine derivative is 1 to 1 based on the total amount of the initial filling oil.
Contains 0 mass% and has an apparent viscosity of 3 to 1 at 25 ° C.
An initial filling oil of 000 mPa · s is used, and the apparent viscosity at 25 ° C. is 1.5 to 40 of the apparent viscosity at 25 ° C. as a rust preventive oil (replenishing oil) for replenishment.
A rust preventive method characterized by using double the amount of replenishing oil. 3. The initial filling oil contains hydrocarbon light oil having a kinematic viscosity at 40 ° C. of less than 10 mm ² / s in an amount of 10 to 90% by mass based on the total amount of the initial filling oil. The rust preventive method according to 1 or 2.