JPH0791550B2 - Anti-rust press working oil for galvanized steel sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to an electrogalvanized steel sheet, a hot-dip galvanized steel sheet,
The present invention relates to a press working oil having both rust-preventive properties (rust proof properties such as white rust and red rust) and discoloration-preventive properties, which are applied to steel plates such as zinc alloy plated steel plates and galvannealed steel plates.

[Prior Art] As a press working oil for galvanized steel sheet, mineral oil, fat and oil,
High-viscosity oil containing a compound of fats and oils is used as a base oil such as liquid synthetic oil, but in press working, the tool temperature is 50 to 100 ° C due to continuous processing, and the processing material Also, since heat is generated due to deformation, the galvanized steel sheet pressed with such processing oil is discolored (darkened), which is not preferable. In addition, since there is no rustproof property during the storage of the material, it is the current situation that white rust easily occurs and, for example, red rust is more likely to occur mainly at the steel plate edge portion during transportation. In addition, it may be difficult to completely remove the press oil film in the degreasing and washing step when chemical conversion treatment is performed on the galvanized steel sheet after pressing as a pretreatment for coating.
Furthermore, if any one of discoloration, white rust, red rust, or a mixture thereof is present on the surface of the steel sheet, there is a problem that the quality of the coating film is significantly impaired due to poor formation in any case.

Next, as a rust preventive oil for galvanized steel sheets, a base oil containing an alkyl sulfonate or a carboxylate is used, but since this oil has poor lubricity, such an oil is galvanized. When pressing a steel sheet, it is necessary to apply a pressing oil on it, so a multi-functional oil for galvanized steel sheet that can impart discoloration resistance, rust prevention and workability with a single application of oil The development request of was generated.

[Problems to be Solved by the Invention] The present invention is excellent in process lubricity, discoloration resistance, rust resistance, and degreasing property in pre-painting treatment by applying oil once as a press working oil for galvanized steel sheet. The present invention provides a rust preventive and press working oil for galvanized steel sheets.

[Means for Solving the Problems] The present inventors have studied press working oils for galvanized steel sheets that can solve the problems described above, and have obtained the following new findings.

(B) In order to maintain appropriate press lubrication performance, the type of sulfur-binding compound, the number of carbon atoms in its molecular structure, the content of inert sulfur, and the amount of sulfur-binding compound compounded in the press oil should be limited. What you need to do.

(B) In order to suppress discoloration of the oil-coated galvanized surface, the sulfur-based extreme pressure agent must be an inactive type and the active sulfur content in the processing oil must be 0.5% or less.

(C) In order to impart white rust resistance and red rust resistance, a compound selected from alkyl sulfonates, caronic acid and its salts, and amine compounds is added to the press oil. In order to maintain proper performance, it is necessary to limit the number of carbon atoms in the molecular structure, the type of salt, and the blending amount in the pressing oil.

(D) When it is necessary to properly maintain the washability of the oil film of the press working oil, limit the viscosity of the base oil to 5 to 30 cst (40 ° C).

The press working oil of the present invention made based on the above knowledge and the technical orientation based on the above knowledge includes (a) a base oil, a rust preventive additive and a lubricating component as essential components (b) As means for limiting the components, base oil: 60 to 95 parts of one or more selected from mineral oil, fats and oils and liquid synthetic oil. To keep the oil film cleanliness and removability moderate, the viscosity of the pressing oil should be 5
Adjust to keep at ~ 30cst.

Rust-preventive agent: anti-rust additives are alkali metal salts of C ₁₆ or higher alkyl sulfonic acid, alkaline earth metal salts, amine salts, C ₁₂ or higher carboxylic acids, alkali metal salts of C ₁₂ or higher carboxylic acids, alkali It is a compound selected from an earth metal salt, an amine salt, and a nitrogen-containing compound, and 1 to 20 parts of these are contained.

Lubricating component: The lubricating component is a sulfur-based extreme pressure agent (inertness 1a or 1b) of an inactive type, is a sulfur-bonding compound containing 5 to 15% of a sulfur content, and is a fat, a fatty acid ester, or
A compound having a sulfur bond between a fat and oil and a C _{8 to} C ₁₈ olefin, and more specifically, a C ₁₂ or higher unsaturated fatty acid and C ₈
A compound selected from those in which an ester compound with the above aliphatic alcohol and a C ₈ or more olefin are sulfur-bonded, and those in which a glycerin ester of a C ₁₂ or more unsaturated fatty acid and a C ₈ or more olefin are sulfur-bonded . These are contained in 1 to 20 parts of one kind or two or more kinds. The classification of the inactive type and the active type is judged by copper plate corrosion according to JIS-K-2513. The active type has a lot of copper plate corrosion and turns black.

The base oil applied to the press oil of the present invention may be any one or two or more selected from mineral oils, fats and oils, and liquid synthetic oils, and does not specify their viscosity. However, the viscosity of the press working oil at 40 ° C. is kept at 5 to 30 cst in order to keep the oil film removability after applying and processing the press working oil appropriately.

If the viscosity is lower than 5 cst, it will be difficult to maintain the amount of oil film required to exert lubrication during press working. In this case, a thickener may be added. Examples thereof include polyacrylic acid ester type, polybutene, and the like. On the other hand, when it is higher than 30 cst, the amount of oil film becomes unnecessarily large, which is uneconomical and the cleaning and removability of the oil film after pressing is deteriorated, which is not preferable. In particular, the oil-removing property of the seam portion of spot welding becomes poor, and the oil seeps out, which adversely affects the surface treatment in the subsequent process.

Next, the alkyl sulfonate added as a rust preventive additive is preferably C ₁₆ or more, and the carboxylic acid or carboxylic acid salt is preferably C ₁₂ or more. If the number of carbons is less than that, the rust preventive effect is insufficient. Specifically, the following compounds can be mentioned.

Examples of the alkyl sulfonates include dinonylnaphthalene sulfonic acid metal salt (Ba, Ca, Zn, Mg, Na etc.), didodecylbenzene sulfonic acid metal salt (Ba, Ca, Zn, Mg, Na).
Etc.), petroleum sulfonic acid metal salt.

C ₁₆ or more carboxylic acid or a salt thereof, for example, isooleic acid, oleic acid, dimer acid, alkenyl succinic acid, petroleum oxide wax or a metal salt thereof (Ba, Ca, Zn, Mg,
Na), and amine salts.

Examples of the nitrogen-containing compound of C ₁₂ or higher carboxylic acids, for example, benzotriazole and C ₁₂ or higher carboxylic acid compound of the imidazoline.

Of the above-mentioned compounds, particularly preferable are barium salt of dinonylnaphthalene sulfonic acid, barium salt of didodecylbenzene sulfonic acid, barium salt of petroleum oxide wax and the like.

One kind or two or more kinds are arbitrarily selected from these compounds and blended in the base oil. The amount of the rust preventive component to be added to the base oil is 1 to 20 parts, and if the amount is less than 1 part, the rust preventive effect will be insufficient, and addition of more than 20 parts cannot be expected to improve the effect.
Due to the balance with other ingredients, the upper limit is 20 parts.

Next, as a lubricating component, it is an inert type sulfur-based extreme pressure agent, and is the following sulfur-bonding compound containing 5 to 15% of sulfur content. That is, fats and oils, fatty esters or oils and C ₈ -C ₁₈
Is a compound having a sulfur bond with the olefin of (1), and more specifically (1) fats and oils are glyceride-based lard oil, rapeseed oil, chicken oil and the like.

General formula R ₁ is mainly composed of C ₁₂ or more unsaturated fatty acids.

The fatty acid ester of (2) is orange raffine oil, oleyl ester of oleic acid, methyl ester of oleic acid and the like.

The general formula R ₁ COOR ₂ R ₁ is the same fatty acid as described above, and R ₂ is a C ₁ or higher aliphatic alcohol.

(3) Compounds having a sulfur bond between an oil and fat and a C ₈ or higher olefin are shown below.

B) R ₁ is a sulfur-bonded product of an ester compound of a C ₁₂ or higher unsaturated fatty acid, R ₂ is an ester of a C ₈ or higher aliphatic alcohol, and R ₃ is a sulfur-bonded product of an C ₈ or higher olefin.

B) R ₁ is a sulfur-bonded product of a glycerin ester of a C ₁₂ or higher unsaturated fatty acid and a C ₈ -C ₁₈ olefin of R ₃ .

Olefins C ₈ -C ₁₈ is made of, for example ethylene or propylene of the polymer.

The active sulfur content in the rustproofing press oil is 0.5% or less, and if it exceeds 0.5%, the reactivity with the zinc surface is too strong, and the discoloration of the surface tends to be strong after processing. 0.3% or less is preferable.

The lower limit of the carbon number is determined in consideration of lubricity, especially when the processing temperature of the galvanized material rises (70 to 100 ° C.).

One kind or two or more kinds are arbitrarily selected from the above sulfur-bonding compounds and blended in the base oil. The compounding amount of the compound is preferably 1 to 20 parts, and if less than 1 part, the lubricating performance becomes insufficient, and it is preferable to set 20 parts as the upper limit in order to prevent discoloration of the galvanized material after pressing.

Next, in order to further improve the lubrication discoloration prevention of the pressing oil of the present invention, a phosphorus-based extreme pressure additive can be added. Furthermore, an oil-soluble surfactant of less than a few% can be added to the pressed oil of the present invention in order to improve the oil film removability of the processed oil, and such addition is not prohibited in the present invention.

The effects of the present invention will be specifically described below with reference to Examples and Comparative Examples.

[Example] Using the sample oil Nos. 1 to 4 of the examples of the present invention shown in Table-1,
It was applied to a test piece by a roll coater method, and the following deep drawing test, rust prevention test and degreasing test were performed. In Table 1, sample oil Nos. 5 to 9 are comparative examples, which were tested in the same manner as in the examples.

The amount of oil applied was adjusted to 1.5 ± 0.1 g / m ² .

1) Lubrication test 1-1) Deep drawing test a. Test piece material: Alloyed hot-dip galvanized steel sheet 50/50 Dimensions: 90mm (diameter) x 0.7mm (thickness) b. Tool die diameter: 42.5mm (diameter) Punch diameter: 40.0mm (diameter) Punch shoulder radius: 8mm c. Test condition Drawing speed: 2mm / sec Wrinkle clamp load: 1,000kg d. Judgment Deep drawing ratio (%) = (1-D / Do) x 100 Do: Diameter of test piece before test D: Average diameter of test piece after test 2) Rust prevention test 2-1) Wet test a .Test piece material: Hot-dip galvanized steel sheet 50/50 Dimensions: 70mm × 150mm × 0.7mm b. Test conditions Wet test method (JIS K 2246 4.32 compliant) Temperature: 49 ± 1 ℃ Relative humidity: 95% or more Time: 240 hours c. Judgment: The degree of discoloration and white rust occurrence of the test piece is judged according to the table below.

2-2) Stack test a. Specimen material: Alloyed hot-dip galvanized steel sheet (50/50) Dimensions: 70mm x 150mm x 0.7mm b. Test conditions Temperature and humidity tester operating temperature: 49 ± 1 ° C Relative humidity: 95% or more Period: 30 days c. Judgment: Judge the discoloration and white rust occurrence of the test piece in the same manner as in the wet test.

3) Degreasing test a. Specimen material: Alloyed hot-dip galvanized steel plate (50/50) Dimension: 70mm × 150mm × 0.7mm b. Adjustment of specimens After applying oil to each specimen, as shown in Fig. 1. Was spot-welded and left to stand in a humid box of 95% or more for 24 hours for aging.

c. Test conditions Degreasing was performed using a spray type degreasing device.

Degreasing agent: Merchandise / Fine Cleaner 4326 [manufactured by Nippon Parkerizing Co., Ltd.] Concentration 2%, temperature 60 ° C, spray pressure 0.5 kg / cm ² d. Judgment Water wet when the test piece after degreasing is washed in running water area(%)
It is represented by.

Next, this test piece is heated at 170 ° C. for 30 minutes, and the oil bleeding from the joined portion is also judged.

As is clear from the results in Table-2, the composition of the present invention comprises
The lubricity, rust prevention and degreasing properties are superior to the comparative examples.

[Effects of the Invention] By using the rust-preventing press working oil for galvanized steel sheet of the present invention, excellent working lubricity, discoloration resistance, and rust resistance can be obtained by one-time application of oil during press working of galvanized steel sheet. And degreasing property can be achieved in the pretreatment of coating.

[Brief description of drawings]

FIG. 1 is a diagram showing spot welding in a degreasing test.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C10M 105: 34 135: 10 135: 06 159: 06) C10N 10:04 20:02 30:02 30 : 12 40:24 Z 60:04 60:10 (72) Inventor Yasuo Okumura 1-151-1 Nihonbashi, Chuo-ku, Tokyo Within Parkerizing Co., Ltd. Japan (72) Inventor Yasuo Tanizawa 1-15, Nihonbashi, Chuo-ku, Tokyo No. 1 in Japan Parkerizing Co., Ltd. (72) Inventor Naoyuki Hayashi 2-15-5 Nihonbashi, Chuo-ku, Tokyo Sugiyama Building Parker Kosan Co., Ltd.

Claims (2)

[Claims] 1. 65 to 95 parts by weight of one or more kinds of oils selected from mineral oils, fats and oils and liquid synthetic oils (parts by weight; hereinafter the same), and 1 to 20 parts of rust preventive additives, 1 to 20 parts of active type sulfur extreme pressure agent, the active sulfur content in the pressing oil is 0.5% or less, and the viscosity is 5 to 30 cst at 40 ° C. For rust prevention and press working oil. 2. An inert sulfur extreme pressure agent comprising a synthetic ester compound, a fat or oil, or a fat or oil containing 5 to 15% of sulfur.
Wherein the C ₈ -C ₁₈ which is an olefin and sulfur bonded to have compounds, galvanized steel sheet for rust combined pressing oil according to claim (1).