JP2003201493A - Rust-preventive oil / pressing oil composition for galvanized steel sheet - Google Patents

Abstract

(57) [Problem] To provide a rust-preventive oil / pressing oil composition for galvanized steel sheets which is excellent in lubricity, corrosion resistance and detergency. SOLUTION: The rust-preventive oil / pressing oil composition for a galvanized steel sheet of the present invention is composed of a base oil, mineral oil, and a total of 1 composition.
It contains 5% by mass of oleylamine, which is an unneutralized oil-soluble amine, and 5% by mass of barium sulfonate and 5% by mass of sulfide ester, respectively, based on 00% by mass. The rust-preventive oil and press-working oil composition for a galvanized steel sheet of the present invention, having such a configuration, has excellent rust-preventive properties and can improve lubricity as compared with conventional ones. Further, by using a low-viscosity mineral oil as the base oil, the cleaning property can be improved. As a result, it can be suitably used for processing of a galvanized steel sheet requiring excellent workability, and can correspond to a high-tensile steel sheet.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rust preventive oil / press working oil composition for galvanized steel sheets, and more specifically, it has excellent lubricity and rust preventive properties and can be applied to high tensile strength steel sheets. The present invention relates to a rust preventive oil / pressing oil composition for galvanized steel sheets, which can also be used as a cleaning oil for galvanized steel sheets.

[0002]

2. Description of the Related Art Conventionally, galvanized steel sheets used for steel sheets for automobiles are rust-prevented for the purpose of rust prevention during storage, movement, etc. after being manufactured through pre-processes such as rolling. It is applied with oil and then subjected to the next step such as pressing. In the next step, rust-preventive oil or stains attached during storage / movement are removed by washing, and then appropriate working oil is applied to carry out processing. However, according to this method, the rust preventive oil applied in the previous step must be removed in the next step, and then the working oil must be applied, which is troublesome.

On the other hand, in press working of a galvanized steel sheet in recent years, in order to simplify the process, it has been performed to give rust preventive oil a performance as a press working oil,
As a result, some rust preventive oils and press working oils have been developed. For example, Japanese Patent No. 304839
No. 7 discloses a lubricant base oil having a specific viscosity range, a sulfur-based extreme pressure additive, a Ca, Ba or Mg salt of a highly basic sulfonate having a total base number within a predetermined range, and a carvone having a predetermined carbon number. Disclosed is a rust preventive oil composition for press working of galvanized steel sheet, to which a rust preventive additive which is an amine salt of an acid is added. Further, in JP-A-2000-319680, components such as an anticorrosive additive, a trialkyltrithiophosphite and an inert sulfur-based extreme pressure additive are added to a base oil, and a trialkyltrithiophosphite and Disclosed is a rust preventive / pressing oil for galvanized steel sheets in which the content of the active sulfur-based extreme pressure additive, the active sulfur content, the saponification value, and the kinematic viscosity are within predetermined ranges.

[0004]

[Problems to be Solved by the Invention] However, today,
Against the background of the weight reduction of automobiles, there is an increasing tendency to reduce the thickness of steel sheets used and improve the strength.
Further, with the diversification of the body shape and the like, it is required to process the steel sheet used into a more complicated shape. From this point of view, further improvement in the processing performance of press working oil is required, but conventional rust preventive oil / press working oil cannot obtain sufficient working performance to meet this, and as a result, press Increasingly, product defects such as scratches and seizures occur on the product surface after processing. Therefore, there has been a demand for a rust preventive oil / press oil having higher lubricity and rust preventive property than the conventional rust preventive oil / press working oil. In addition, when manufacturing automobiles, cleaning oil for galvanized steel sheets called leveler cleaning oil is used to wash off stains and excess rust preventive oil that have adhered to the steel sheet immediately before pressing. It has been desired to develop a rust preventive oil / pressing oil for galvanized steel sheets with high lubricity that can be applied.

The present invention has been made in view of the above circumstances and is excellent in lubricity and anticorrosiveness, can be applied to high-tensile steel sheets, and can be used as a cleaning oil for galvanized steel sheets. An object is to provide a rust oil / pressing oil composition.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the relationship between composition components and performance of a rust preventive oil / pressing oil composition for galvanized steel sheet, and as a result, found that a water-insoluble base oil. By adding an unneutralized oil-soluble amine to general rust-preventing oils containing as a main component, it has excellent rust-preventing properties and also has better lubricity than before. The present invention was completed by finding that an oil composition was obtained, and that by using a water-insoluble low-viscosity base oil, this composition also had excellent detergency.

The rust preventive oil / press working oil composition for galvanized steel sheet of the present invention is characterized in that the base oil contains an unneutralized oil-soluble amine. The carbon number of the organic group contained in the oil-soluble amine can be 6 to 22. Further, the content of the oil-soluble amine is 0.1% in 100% by mass of the rust preventive oil / press working oil composition for galvanized steel sheet.
It can be up to 20% by mass. Further, the rust preventive oil / pressing oil composition for galvanized steel sheet of the present invention may further contain a sulfur compound. Further, the rust preventive oil / press working oil composition for galvanized steel sheet of the present invention can be used as an oil for cleaning galvanized steel sheet. In that case, the viscosity of the base oil at 40 ° C. is 10 mm ² / s.
It can be less than.

[0008]

EFFECTS OF THE INVENTION The rust preventive oil / press working oil composition for galvanized steel sheet of the present invention contains unneutralized oil-soluble amine, and thus has excellent rust preventive property and excellent lubricity as compared with conventional ones. Play. Therefore, the press workability is superior to the conventional one, and it can be applied to the high-tensile steel plate. In particular, by using a sulfur compound together, the lubricity can be further improved. Further, the rust preventive oil / pressing oil composition for galvanized steel sheet of the present invention, by using a low viscosity base oil, exhibits excellent detergency in addition to the above-mentioned characteristics, so that the viscosity of the composition is appropriately selected. By doing so, it can also be suitably used for washing off stains and excess rust-preventing oil adhering to the steel sheet immediately before pressing.

[0009]

The present invention will be described in more detail below. (1) Base oil The base oil of the present invention can be used without particular limitation as long as it is water-insoluble and is used as a base oil for general rust preventive oils. In addition, any composition can be used as long as it does not deteriorate the press workability and rustproofness of the composition. Specific examples of the base oil include kerosene, light oil, spindle oil, machine oil, neutral oil, turbine oil, cylinder oil, mineral oil such as liquid paraffin, beef tallow, lard, rapeseed oil, coconut oil, palm oil. , Oils and fats such as nuka oil and hydrogenated oils thereof, fatty acids obtained from the oils and fats, synthetic ester compounds (esters of fatty acids and alcohols, polyol esters, etc.), poly α-olefins (boribten, etc.), isoparaffin, n
Hydrocarbons such as paraffin or synthetic hydrocarbons, alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, polyoxyalkylene glycol ethers, silicone oils, polyols such as polyethylene glycols, polyethers or polyesters and synthetic lubricating oils such as higher alcohols, A petroleum solvent or the like can be used. The base oil of the present invention may be composed of only one type, or may be used in combination of two or more types.

The properties of the base oil of the present invention are not particularly limited, and base oils having various properties can be used as required. For example, the viscosity of the base oil is not particularly limited, but the viscosity at 40 ° C. is 10 mm ² / s.
Less than, preferably 8 mm ² / s or less, more preferably 5
It is preferable to use a low-viscosity base oil having a viscosity of mm ² / s or less, and more preferably 4 mm ² / s or less, because the cleaning property can be improved while maintaining excellent lubricity.

(2) Oil-soluble amine The above-mentioned oil-soluble amine of the present invention has an organic group, and if it is an amine which is stably mixed, dissolved and dispersed in the water-insoluble base oil, its structure and the like are There is no particular limitation. For example, the oil-soluble amine may be any of primary amine, secondary amine and tertiary amine, and the number of amino groups is 1.
One, two or more. Further, the organic group constituting the oil-soluble amine usually has 6 to 22 carbon atoms, preferably 10 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
Is an organic group. When the carbon number of the organic group is within the above range, it is possible to stably mix, dissolve and disperse in the water-insoluble base oil, which is preferable. Further, when there are a plurality of the above organic groups constituting the above oil-soluble amine, each organic group may be the same group or different groups. Further, the above organic group may contain not only a hydrocarbon group but also other functional groups as long as the object of the present invention is not impaired. The oil-soluble amine of the present invention may be used alone or in combination of two or more.

The oil-soluble amine of the present invention needs to be unneutralized. If the "oil-soluble amine" is neutralized, the effect of improving lubricity is impaired, which is not preferable. Here, "unneutralized" includes not only the case where no neutralization is carried out at all, but also the case where a partially neutralized but unneutralized oil-soluble amine is present in the system.
In this case, the proportion of the unneutralized oil-soluble amine in the total oil-soluble amine is usually 60% or more, preferably 70% or more, more preferably 80% or more, particularly preferably 85% or more, most preferably 90%. That is all.

Specific examples of the oil-soluble amine include octylamine, laurylamine, decylamine, laurylamine, stearylamine, dioctylamine, dilaurylamine, didecylamine, dilaurylamine, distearylamine, trioctylamine, Primary, secondary and tertiary linear saturated alkylamines such as trilaurylamine, tridecylamine, trilaurylamine and tristearylamine, oleylamine,
Primary such as dioleylamine and trioleylamine,
Secondary and tertiary unsaturated alkylamines, 2-ethylhexylamine, isostearylamine, di (2-ethylhexyl) amine, di (isostearyl) amine,
Primary, secondary and tertiary branched alkylamines such as tri (2-ethylhexyl) amine and tri (isostearyl) amine, primary such as cyclohexylamine, dicyclohexylamine and tricyclohexylamine,
Primary, secondary and tertiary aromatic amines (including heterocyclic compounds) such as secondary and tertiary alicyclic amines, benzylamine, dibenzylamine and tribenzylamine
Etc.

In the present invention, the content of the oil-soluble amine is not particularly limited, and various contents can be set as necessary. Usually, 0.1 to 20 in 100% by mass of a rust preventive oil / pressing oil composition for galvanized steel sheet
%, Preferably 0.15 to 15% by mass, more preferably 0.2 to 10% by mass. When the content of the “oil-soluble amine” is 0.1% by mass or more, the effect of improving the lubricity becomes large, which is preferable. On the other hand, even if the content of the “oil-soluble amine” exceeds 20% by mass, the effect of improving lubricity cannot be expected any more, and it is uneconomical. Therefore, it is economical to set the content to 20% by mass or less. Is preferred.

(3) Sulfur-based compound In the present invention, a sulfur-based compound can be further added in addition to the oil-soluble amine. The combined use of such a sulfur-based compound is preferable because the lubricity can be further improved. The sulfur-based compound is not particularly limited as long as it is a compound containing a sulfur atom, for example, sulfurized mineral oil, or sulfurized fat oil such as sulfurized pig oil, sulfurized beef tallow, sulfurized rapeseed oil, sulfurized oleic acid, sulfurized linoleic acid. And sulfurized fatty acids, sulfurized methyl oleate, sulfurized methyl linoleate, and other sulfurized esters, alkyl disulfides, alkyl trisulfides, and other polysulfides, and the like. In addition to these, sulfonates such as alkyl sulfonate and alkyl phenyl sulfonate, and salts thereof,
Examples thereof include dithio compounds such as zinc alkyldithiophosphate (ZnDTP) and zinc alkyldithiocarbamate (ZnDTC). Of these, sulfurized mineral oil, sulfurized fatty oil, sulfurized fatty acid, sulfurized ester, and polysulfide are particularly preferable because the lubricity can be further improved. The above sulfur-based compounds of the present invention may be used alone or in combination of two or more.

In the present invention, the content of the above-mentioned sulfur-based compound is not particularly limited, and various contents can be set as necessary. Usually, it is 1 to 40% by mass, preferably 3 to 30% by mass, more preferably 5 to 2 in 100% by mass of the rust preventive oil / pressing oil composition for galvanized steel sheet.
It is 5% by mass. The content of the sulfur-based compound is 1% by mass
It is preferable for the above to be large because the effect of improving lubricity is great. On the other hand, even if it exceeds 40% by mass, the effect of improving lubricity cannot be expected any more, and it is uneconomical. Therefore, it is economically preferable to set it to 40% by mass or less.

Further, in the present invention, any component used in a general rust preventive oil / pressing oil can be used without any particular problem as long as the object of the present invention is not impaired. For example, neutral and highly basic alkyl sulfonic acid alkali metal salts, neutral and highly basic alkyl sulfonic acid alkaline earth metal salts, neutral and highly basic alkyl benzene sulfonic acid alkali metal salts, neutral and highly basic Basic alkylbenzene sulfonic acid alkaline earth metal salt, neutral and highly basic carboxylic acid alkaline metal salt, neutral and highly basic carboxylic acid alkaline earth metal salt, oxidized wax and its derivatives, petroleum wax and the like Derivatives, animal and vegetable waxes and their derivatives, esters of monohydric or polyhydric alcohols, partial esters of monohydric or polyhydric alcohols and the like can be used. In addition, for example, if necessary, it is possible to appropriately add optional components such as a defoaming agent, a non-ferrous metal anticorrosive agent, a pour point depressant, a viscosity index improver, a fragrance, a dye, a pigment, an antiseptic and a bactericide. Is. In the present invention, the presence of an excessive amount of an acidic substance such as a free carboxylic acid neutralizes the oil-soluble amine and loses its effect, which is not preferable, but unneutralized oil-soluble amine is present in the system. In the present invention, an acidic substance such as a free carboxylic acid can be added if it is restricted so that it is present.

The rust preventive oil / press working oil composition for galvanized steel sheet of the present invention is excellent in lubricity by containing the unneutralized oil-soluble amine, and the conditions and measurement described in the following examples are carried out. In the Bowden test measured by the method, the average friction coefficient is 0.20 or less, more preferably 0.
It can be 15 or less, more preferably 0.13 or less. Also, in the draw beat test, pulling force is 55
It can be 0 kg or less, more preferably 510 kg or less, and further preferably 500 kg or less. Further, the galvanized steel sheet anti-rust oil and press working oil composition of the present invention,
By providing the above-mentioned structure, even if it is a cleaning oil used to easily wash off stains and excess rust-preventing oil that have adhered to the steel sheet immediately before pressing using a low-viscosity base oil, the lubricity is almost reduced. Can be used without.

[0019]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. (1) Preparation of anti-corrosion oil / pressing oil composition for galvanized steel sheet In 100 mass% of anti-corrosion oil / pressing oil composition for galvanized steel sheet, the following components are blended in a ratio of mass% shown in Table 1. By doing so, rust preventive oil / pressing oil compositions for galvanized steel sheets of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared.
As the rust preventive oil / pressing oil composition for galvanized steel sheet of Comparative Example 4, “Yushiron Former CF6010” manufactured by Yushiro Chemical Co., Ltd. was used. The viscosity at 40 ℃ ^(mm 2 / s) is Cannon - with Fenske viscometer, was measured according to JIS K2283. (A) Oleylamine; trade name "Amine OB" (manufactured by NOF Corporation). (B) Sulfated ester; used in-house synthesized product (c) Barium sulfonate; Trade name "Surchem
404 "(manufactured by Witco, base number about 10 mg / KO
H) (d) sorbitan ester; trade name "IONET S8
5 ”(manufactured by Sanyo Kasei Co., Ltd.) (e) Mineral oil A; trade name“ spindle oil ”(manufactured by Cosmo Oil Co., Ltd.) viscosity 10 mm ² / s (40 ° C.) (f) mineral oil B; trade name“ solvent No7 ” (Exxon Chemical Co., Ltd.) Viscosity 2 mm ² / s (40 ° C.)

[0020]

[Table 1]

(2) Performance Evaluation Lubricating by the following Bowden test and draw beat test using the rust preventive oil / pressing oil composition for galvanized steel sheets of Examples 1 to 7 and Comparative Examples 1 to 4 above. The sex was evaluated. In addition, rust prevention was evaluated by the salt spray test and the wet test shown below. The results are also shown in Table 1 above.

(A) Bowden test A rust preventive oil / pressing oil composition for galvanized steel sheet of each of Examples 1 to 7 and Comparative Examples 1 to 4 was applied on a test piece which was a galvanized steel sheet (GA material). , Followed by SUJ2 3 /
Using a 16-inch test ball, the test piece was slid 20 times at a temperature of 50 ° C. under a load of 1 kg. And 2
The lubricity of the rust preventive oil / press working oil compositions for galvanized steel sheets of Examples 1 to 7 and Comparative Examples 1 to 4 was evaluated by calculating the average friction coefficient when sliding zero times. . The evaluation was excellent (⊚) when the average friction coefficient was less than 0.10.
Less than 15 is good (○), less than 0.20 is bad (△),
Table 1 shows that 0.20 or more was unusable (x).

(B) Drawbeat test plate A 1 mm thick galvanized steel sheet (GA material) on a test piece is used as the rust preventive oil and press working oil for the galvanized steel sheets of Examples 1 to 7 and Comparative Examples 1 to 4 above. The composition was applied, and subsequently, the pulling force for pulling out the test piece was measured by a load cell under the conditions of pressing pressure of 400 kgf and pulling speed of 0.1 m / min. The evaluation is shown in Table 1 with a drawing force of less than 480 kg as excellent (⊚), less than 530 kg as good (∘), and 530 kg or more as unusable (x).

(C) Salt Spray Test and Wet Test JIS K2246 "Salt Spray Test" and JIS K2246
The test was performed according to the "wetting test" of 2246. In the evaluation, there is no rust, “⊚”, the area of the rust occurrence portion is “O” for 1 to 10% of the total area of the test piece, and the area of the rust occurrence portion is “X” for 11 to 25% of the total area of the test piece, Table 1 shows that the area of the rusted portion is 26% or more of the total area of the test piece as "XX".

(D) Immersion of a steel sheet coated with mineral oil in which detergency fine iron powder is dispersed into the rust preventive oil / pressing oil composition for galvanized steel sheets of Examples 1 to 7 and Comparative Examples 1 to 4 above. And stir the liquid at 40 ° C.
The detergency was evaluated by examining the removability of contaminants after standing for 3 minutes. The evaluation was “◎” when there was no residual dirt substance and the cleaning property was very good, “○” when there was almost no residual dirt substance and the cleaning property was good, and there was no residual dirt substance. There is a slight amount and the cleaning property is a little bad, and it is "△".
Is shown in Table 1.

(3) Effects of Examples As shown in Table 1, rust preventive oil / pressing oil compositions for galvanized steel sheets of Examples 1 to 7 to which oleylamine which is an unneutralized oil-soluble amine was added. Shows a low coefficient of friction of 0.09 to 0.14 by the Bowden test and a pulling force of 470 to 510 kg by the draw bead test, which means that they all show good lubricity. Further, in both the salt spray test and the wet test, there was no corrosion or almost no corrosion, so it can be seen that excellent corrosion resistance is exhibited. Therefore, it is understood that the rust preventive oil / press working oil composition for galvanized steel sheets of the present example is excellent in lubricity and rust preventive property. Particularly, in Example 4 in which the sulfur-based compound was added,
Even if the amount of oleylamine was smaller than those of Examples 1 to 3, the amount was the same as that of Examples 1 to 3, or showed slightly excellent lubricity and rust preventive property, and the amount of oleylamine was the same as that of Example 2. Shows that the friction coefficient in the Bowden test was 0.09 and the pulling out force in the draw bead test was 470 kg, which were smaller than those of Example 2 in which no addition was made, indicating that further improvement in lubricity is recognized.

On the other hand, the rust preventive oil / pressing oil compositions for galvanized steel sheets of Comparative Examples 1 to 3 to which oleylamine was not added had a coefficient of friction of 0.15 to 0.15 according to the Bowden test.
0.25, pull-out force by draw bead test is 560-6
Since the value is as large as 00 kg, it can be seen that the lubricity is inferior to that in the above-mentioned embodiment. Particularly, in Comparative Example 1 containing no oleylamine and sulfur-based compound, the lubricity is extremely poor. In addition, Comparative Examples 1 and 2
In, the stick beat was seen in the draw beat test. In addition, in Comparative Examples 2 and 3, the lubricity is slightly improved by adding the sulfur-based compound, but it can be seen that the rust preventive property is significantly reduced. Similarly, it can be seen that the commercially available Comparative Example 4 has a lower rust preventive property than the above Examples.

Further, from Table 1, each of the rust preventive oil / pressing oil compositions for galvanized steel sheets of Examples 1 to 7 is superior in cleanability to Comparative Example 4 which is a commercial press oil,
It can be seen that it has better cleaning properties than conventional press oils. Particularly, in Examples 6 and 7 in which the base oil was the low-viscosity mineral oil B, the lubricity and the rust preventive property were almost the same as those in Examples 1 to 5 and the stain removability was higher than that in Examples 1 to 5. It turns out that is good. From the above, each rust-preventing oil / pressing oil composition for galvanized steel sheet of the present invention is excellent in well-balanced all properties of lubricity, rust-prevention property and detergency by having the above-mentioned constitution. I know there is.

The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application. That is,
The rust preventive oil / pressing oil composition for galvanized steel sheet of the present invention is not limited to the composition and the compounding ratio shown in Table 1, and the composition may have various compositions and compounding ratios within the scope of the present invention. can do.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C10M 135/06 C10M 135/06 135/10 135/10 135/18 135/18 135/20 135/20 137 / 10 137/10 A // C10N 20:02 C10N 20:02 30:00 30:00 Z 30:12 30:12 40:24 40:24 ZF term (reference) 4H104 BE02C BE03C BE06C BE07C BG02C BG04C BG06C BG10C BG11 BH07C DA02A DA06A EA02A EB02 LA06 PA23

Claims (6)

[Claims] 1. A rust preventive oil / press working oil composition for galvanized steel sheet, characterized in that an unneutralized oil-soluble amine is contained in a base oil. 2. The rust preventive oil / press working oil composition for galvanized steel sheet according to claim 1, wherein an organic group contained in the oil-soluble amine has 6 to 22 carbon atoms. 3. The galvanized steel sheet according to claim 1, wherein the content of the oil-soluble amine is 0.1 to 20 mass% in 100 mass% of the rust preventive oil / press working oil composition for galvanized steel sheet. Anti-rust oil and press working oil composition for use. 4. The rust preventive oil / press working oil composition for galvanized steel sheet according to claim 1, further comprising a sulfur compound. 5. The rust preventive oil / pressing oil composition for galvanized steel sheet according to claim 1, which can be used as an oil for washing galvanized steel sheet. 6. The base oil has a viscosity of 10 m at 40 ° C.
The rust preventive oil / pressing oil composition for galvanized steel sheet according to claim 5, which is less than m ² / s.