JP2919995B2 - Rust-preventive oil for both press working - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to various kinds of steel sheets used mainly in the automobile industry and the home appliance industry, in particular, surface-treated thin steel sheets such as electrogalvanized steel sheets, galvanized steel sheets, and galvannealed steel sheets. The present invention relates to a press-workable rust-preventive oil having both rust-preventive properties during storage of a steel sheet and suitable formability during press-work.

[0002]

2. Description of the Related Art From the time when a surface-treated steel sheet is manufactured by a steel maker until the time when it is formed and processed into automobiles and home appliances by consumers, the most important point in terms of quality is prevention of rusting. . For this reason, in a normal thin sheet surface-treated steel sheet manufacturing process, immediately before winding on a coil or immediately before cutting into a sheet at the exit side of the final threading line, one of a coating roll method, an oil application method, an electrostatic coating method, etc. Apply an appropriate amount of rust-preventive oil according to the purpose and application according to the method described in The first requirement is that the rust preventive oil can completely prevent rusting immediately before the use of the surface-treated steel sheet, but it is premised that the rust preventive oil can be sufficiently degreased in the degreasing step before the chemical conversion treatment at the time of use. The surface-treated steel sheet coated with anti-rust oil, which is considered to be optimal, is strictly packed with rust-proof paper or polyethylene film laminated with vaporizable rust-proof paper or polyethylene film, and stored in a warehouse until shipped. . The shipped coil or sheet is pressed into a product shape by the user.
The actual press working is a working method in which deformations such as overhang, pulling and drawing are combined in a complicated manner. Therefore, it is necessary to design the material of the surface-treated steel sheet according to the shape, and it is an important technical point to keep the interface between the forming die, the tool and the surface-treated steel sheet in an appropriate lubricated state. If the lubricity is insufficient, press cracks, scratches, wrinkles, etc. will occur on the surface-treated steel sheet side, and scratches will occur on the processing mold. Alternatively, abrasion powder generated by the mold biting the surface of the surface-treated steel sheet accumulates, causing a problem called a star. Further, even if the lubrication is insufficient, various troubles occur depending on the molding conditions. Although various conventional techniques have been devised for this lubrication technique, the most common is wet lubrication in which a mixture of fats and oils and mineral oil is directly applied.
In recent years, with the rationalization of press work by mechanization,
Spray lubrication of press working oil to lubricating parts has been replaced, but it is necessary to select various lubricating oils depending on the type of processing material, mold, tool, etc., it is difficult to control the amount of application, oil consumption by surplus oil Problems such as deterioration of work environment. Solving these various problems and streamlining the process is a great advantage for the steel and automotive industries, and treating rust prevention and press working with a single lubricant is an important issue. It is. In general, rust preventive oils used for surface-treated steel sheets have good degreasing properties and relatively low viscosity (20 mm ² / sec) for reasons such as coil slip prevention.
(40 ° C. or less). However, since the viscosity is low, the oil film strength is low and the lubricity in press working is insufficient. When reducing the viscosity of the press working oil to the same level as that of the rust-preventive oil, the addition of an extreme pressure agent is indispensable in order to increase the lubricity in the press working. Extreme pressure agents used for plastic working, including general press working, are corroded on the surface of the surface-treated steel sheet because processing is continuous, and there is heat generation due to plastic deformation of the sheet material and friction with the mold. Or they tend to discolor. It is difficult to suppress this with a corrosion inhibitor and the utility is poor. That is, it is difficult to satisfy both the rust prevention property and the pressability of the surface-treated steel sheet with either the rust-preventive oil or the press oil using the current technology.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to apply a single coating of rust preventive oil on a surface-treated steel sheet, and to perform press-forming workability, oil stain resistance, rust preventive property, and cleaning by pre-coating treatment. An object of the present invention is to provide a rust-preventive oil for both press working and surface treatment of a surface-treated steel sheet having excellent degreasing properties.

[0004]

According to a first aspect of the present invention, there is provided a base oil comprising: (1) at least one press selected from the group consisting of an alkali metal salt and an alkaline earth metal salt of an alkyl acid phosphate ester; 1 to 5 parts by weight, preferably 2 to 3 parts by weight, (2) at least one oil stain inhibitor selected from the group consisting of alkylbenzotriazoles and arylbenzotriazoles 0.1 to 1 part by weight (3) at least one rust preventive additive selected from the group consisting of an alkali metal salt and an alkaline earth metal salt of an overbased alkylsulfonic acid; Parts by weight, preferably 20 to 40 parts by weight. (4) From the group consisting of carbonates and oxides of alkali metals and alkaline earth metals whose main component is particles of 1 μm or less. At least one solid lubricant 1-10 parts by weight Barre depend, preferably (at 40 ° C.) 2 to 4 parts by weight, is contained, and a viscosity of 5 to 40 mm ² / sec, preferably 15 to 20 mm ² / The present invention relates to a rust-preventive oil for both press working and characterized in that the rust-preventing oil is adjusted to a temperature of 40 sec. A second aspect of the present invention is to provide the base oil with 1 to 5 parts by weight of at least one pressability improving aid selected from the group consisting of an alkali metal salt and an alkaline earth metal salt of an alkyl acid phosphate. (2) 0.1 to 1 part by weight of at least one oil stain inhibitor selected from the group consisting of alkylbenzotriazoles and arylbenzotriazoles; (3) alkali metal salts and alkaline earths of overbased alkylsulfonic acids 5 to 50 parts by weight of at least one rust preventive additive selected from the group consisting of metal salts; (4) From alkali metal and alkaline earth metal carbonates and oxides containing particles of 1 μ or less as main components. 1 to 10 parts by weight of at least one solid lubricant selected from the group consisting of (5) (a) a saturated or unsaturated fatty acid having 12 or more carbon atoms, and (b) Aliphatic polyols, depending from the group consisting of partial esters of barre was at least one oiliness improver 1-2
The present invention relates to a rust preventive oil for press working, characterized by containing 0 parts by weight, preferably 5 to 10 parts by weight, and adjusting the viscosity to 5 to 40 mm ² / sec (at 40 ° C.). When the amount is less than the above-mentioned prescribed amounts (1) to (5), lubricity in press forming cannot be ensured, and when it exceeds, the oil stain property is significantly reduced. The base oil is not particularly limited, but preferably contains 50 to 80 parts of one or more selected from mineral oils, esters and synthetic base oils. The alkyl acidic phosphoric acid ester for forming the metal salt of the alkyl acidic phosphoric acid ester of (1) is a partial alkyl ester such as phosphorous acid, phosphoric acid, or pyrophosphoric acid. the number C ₁₀ -C _22, preferably a linear or branched alkyl of C ₁₆ -C ₁₈ can be used. Specific compounds include stearyl acid phosphate, oleyl acid phosphate, and the like. Specific examples of the alkylbenzotriazole and arylbenzotriazole as the oil stain inhibitor (2) include methylbenzotriazole and methylbenzimidazole. The overbased alkyl sulfonate (3) is an alkyl sulfonate having a total base number of 200 mgKOH / gr or more, and the alkyl has 12 to 30, preferably 18 to 26, C atoms. Dinonylnaphthalene sulfonic acid metal salts (Ba, Ca, Z
n, Mg, Na, etc.), metal salts of didodecylbenzenesulfonic acid (Ba, Ca, Zn, Mg, Na, etc.), and metal salts of petroleum sulfonic acid. The solid lubricant is preferably an oxide of an alkali / alkaline earth metal salt of carbonic acid or an alkali / alkaline earth metal salt having a particle size of 1 μm or less as a main component. When a solid lubricant is added to the rust preventive oil, the dispersion stability in the oil may be deteriorated due to the size of the particle size or due to secondary aggregation. This may cause the lubricating components to separate and settle during storage and cause insufficient lubrication, or when applied to a metal surface, the solid lubricant may become a nucleus of rust generation and significantly reduce rust prevention. The solid lubricant used in the present invention can be uniformly dispersed in oil by the synergistic effect of the overbased sulfonate and the metal alkyl phosphate. Extreme pressure additives, such as sulfur and halogen compounds, chemically react with the metal of the surface-treated steel sheet by heat generated during press working to form an extreme pressure coating, and this coating performs lubrication. That is, since the formation of the lubricating coating depends on the temperature of the lubricating point, if the temperature is low, the lubricating coating is not formed, and the lubricity as expected cannot be secured. On the other hand, if the temperature is too high, the chemical reaction between the extreme pressure agent and the metal may proceed too much, possibly causing discoloration and corrosion of the surface of the surface-treated steel sheet. In the case of the solid lubricant of the present invention, the extreme pressure coating is formed not by a chemical reaction but by physical adsorption, and the adsorbed film has lubricity higher than that of the lubricating film, and has anti-rust and degreasing properties An additive that does not adversely affect oil stain resistance and the like. The component (a) in the oiliness improver (5) is an aliphatic carboxylic acid having a C number of 12 or more.
Oleic acid, stearic acid, lauric acid and the like can be mentioned. The component (b) is a polyol having 4 to 12 carbon atoms and includes glycerin, trimethylolpropane, and pentaerythritol.

[0005]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples.
I will explain. Table I shows the test oil Nos. Of the examples of the present invention.
Apply to test specimen by roll coater method using 1-4
Then, a test was performed by the following method to evaluate the performance. What
In Table I, the test oil No. 5 to 9 are comparative examples, similar to the examples.
Was evaluated. The application amount of the test oil is 1.5 ± 0.2 g
/ M^TwoWas adjusted. Description of test method 1) Lubricity test 1-1) Deep drawing test a. Testing machine Automatic hydraulic thin plate universal testing machine A-12 (Roelunt Korthaus K.G. Solingen-OHLIGS) b. Test piece Material: Galvannealed steel sheet (GA60 / 60) Weight per side 60g / m^Two  Dimension: 90mmφ x 0.7mm thickness c. Tool The tool shown in FIG. 1 was used. Die diameter (Dd): 34.9 mm Die shoulder radius (rd): 3.0 mm Punch diameter (Dp): 33.0 mm Punch shoulder radius (rp): 4.0 mm d. Test conditions Drawing speed: 3 mm / sec Wrinkle holding load (H): 500 kgf e. Measurement The diameter of the blank is changed stepwise, and the drawing ratio at that time = Db / Dd is determined. Dd: die diameter Db: diameter of test piece 1-2) Four-ball test a. Testing machine Four-ball lubrication testing machine (Soda type) b. Rust ball for test Ball for steel for ball bearing SUJ2 3/4 "c. Test conditions Spindle speed: 200 rpm Oil volume: 50 ml Load: 0.5 to 10 kgf / cm^Two  d. Measurement Three steel balls are set in the test oil container and one steel ball is set in the vertical spindle.
Cut. Put the test oil in a container. Apply a load to the steel ball while rotating the main shaft. (0.5kgf / cm^Two/ Min) Operate continuously to withstand load pressure (seizing load
Weight). 1-3) Slidability test a. Test piece Material: Galvannealed steel sheet (GA60 / 60) Weight per side 60g / m^Two  Dimensions: 0.7t x 20W x 350L mm b. Tool Material: SKD11 Dimension: A tool shown in FIG. Contact length with material: 10 mm Inlet radius: 5 mm c. Test conditions Sliding speed: 20 mm / sec Sliding distance: 50 mm Surface pressure: 1 kgf / mm^Two  Tool temperature: 22.75 ° C Based on room temperature (22 ° C), high for evaluation of some lubricating oils
A test at temperature (75 ° C.) was performed. d. Application of test oil Test rust preventive oil is 1.5 ± 0.2 g / m per side of test piece^Two
Apply. e. Test method The test piece shown in FIG.
P (contact pressure 1kgf / mm^Two), And in that state
Pull out the test piece and measure the pulling load D at that time
I do. Both P and D were measured with a load cell, and
To determine the coefficient of friction.2) Rust prevention test 2-1) Common items a. Dimension of test piece The test piece shall be 60W x 80L x 0.7t mm
Two holes (2 mmφ) were drilled at both ends of the long side. b. Washing method of test piece Hot petroleum naphtha, hot anhydrous methanol
Soak in order and wipe until the gauze is no longer soiled. c. Application of test oil Test rust preventive oil applied to test surface at 1.5 ± 0.2 g / m^TwoApply
You. Predetermined application to test specimens weighed in test rust preventive oil
It was applied with a roll coater and the weight was measured. The following calculation
The oil application amount was determined from the equation.d. Number of test pieces Except for the oil stain test, the number of test pieces repeated (n number)
Is three. 2-2) Oil stain resistance test a. Stacking method of test specimens 7.5W × 60L ×
A Teflon spacer of 0.1 t (mm) was sandwiched. Next, clip four pieces of the sample (Lion binder
-Clip No. 111). Finally, a slip
(No. 5C) and according to JIS K 2246
Packaged. b. Corrosion test method In the test, the test piece was placed in a constant temperature and humidity chamber with the test piece horizontal. Test conditions: temperature 60 ± 1 ° C, humidity 95% RH, 30
Went for days. c. Judgment method After the test, the sample was left to reach room temperature and opened. The test piece after opening is immediately visually inspected according to the following criteria.
Make a decision. The degree of rust occurrence is determined by the grid method according to JIS K 2246.
You. Includes all red rust, black rust and white rust. The criteria are shown in Table 1.
You.

[Table 1] 2-3) MIL oil stain test (MILC 222)
35A) 5% of water is added to the test oil to forcibly emulsify it, and this is applied to a test piece. Observe the state of occurrence of oil stain on the surface of the overlapping portion. a. Test conditions Temperature: 80 ° C Time: 24 hr Load: 100 g b. Test piece combination: KTUX / KTUX KTUX / GA GA / GA KTUX / EG EG / EG 2-4) Chlorine corrosion resistance test (atmospheric exposure test) a. Sample preparation method KCl is mixed and dissolved in water-ethanol so that the chlorine concentration becomes 500 ppm. The test piece was immersed in this KCl solution for 10 seconds, pulled up and dried with warm air. Subsequently, 2-1) c. The test oil was applied by the method specified in the section. b. Corrosion test method The test piece was installed at an angle of 60 degrees with respect to the horizontal plane, facing south in an outdoor one hundred box (product of the Japan Meteorological Association). The condition of the specimen was observed and recorded on Monday, Wednesday and Friday. At the same time, change the installation position of the test piece to forward. c. Test period The period until the occurrence of rust on at least 50% of the area of two or more test pieces with the slowest rust generation among the rust preventive oils subjected to the test. d. Judgment method The condition of the test specimen was observed on Monday, Wednesday and Friday, and when rust was observed on two or more of the specified comparative oil-coated test specimens, J
The area of rust generation was determined by the grid method of IS K2246.
2-4) c. After the period specified in, the same determination as above was performed. 2-5) Chlorine corrosion resistance test (accelerated test) a. Test piece preparation method 2-1) c. Test pieces coated with rust-preventive oil were prepared by the method specified in the section. 1 g of the dust containing KCl prepared in the following manner is evenly adhered to the test piece of 1). <Dust preparation method> JIS 11 type standard dust was placed in a saturated KCl aqueous solution, mixed and stirred, and then the dust was drained and dried with hot air. Thereafter, the mixture was sieved to a particle size of 300 to 500 μm. b. Corrosion test method Specimens were placed horizontally in a thermo-hygrostat. Temperature 60 ±
This is performed for 30 days at 1 ° C. and 95% RH. c. Judgment method Test pieces were taken out on days 10, 20, and 30, and after washing, J
The corrosion state was visually determined by a grid method specified in ISK2246. 2-6) Atmospheric exposure test A test oil-coated steel plate that is set upright on a wooden frame as shown in Fig. 2 is exposed under the eaves, and changes in the appearance of the coating film and rust generation are observed. Test conditions Time: 30 days 2-7) Zinc dissolution test 70 ml of rust-preventive oil was collected in a 100 ml beaker, and two L-shaped test pieces (30 × 60) were measured in advance. One was bent on the plating side and the other was bent on the cold-rolled steel sheet side, and the amount of zinc eluted in the oil was measured, such as weight change and discoloration of the test piece after leaving at 80 ° C. for 2 weeks. 3) Degreasing test 3-1) Common matters a. Dimension of test piece 2-1) a. Same as b. Method of cleaning test piece 2-1) b. Same as c. Application of test oil 2-1) c. Same as d. Number of test pieces The number of test piece repetitions (n number) is 10. e. Preparation method of degreasing solution Using distilled water, the degreasing agent Ridolin SD400A is 1.5
A solution containing 0.5% by weight of SD400B was prepared. 0.5 wt% of a test rust preventive oil was added to the solution and stirred to obtain a test degreasing solution. f. Degreasing test method 3-1) e. While stirring the fat-free solution prepared in
When the temperature rises to ± 2 ° C and reaches the specified temperature, the test specimen is immersed and degreased for
Then, it was washed with tap water. g. Judgment method f. Immediately after the operation, the test piece was immediately immersed in distilled water for 1 second, the test piece was taken out vertically, and the state of water leakage after 30 seconds was visually observed. Table 2 shows the criteria.

[Table 2] 3-2) Initial degreasing test a. Test method 2-1) c. The test specimen coated with the test oil by the method specified in the section is left indoors for 24 hours. 3-1) f. Perform the degreasing test specified in the section. 3-3) Degreasing test over time a. Packaging method of test piece 2-1) c. Lay 10 test pieces coated with the test oil by the method specified in the section. The above-mentioned materials were packed in accordance with JIS K 2246 using PE laminated paper with the PE side facing out. b. Storage method The sample was placed horizontally in a constant temperature and humidity chamber. It was left for 30 days at a temperature of 60 ± 1 ° C. and a humidity of 95% RH. c. Test method After leaving for a specified period, the sample was opened at room temperature and left indoor for 24 hours. Thereafter, 3-1) f. The degreasing test specified in the section was performed. 4) Chemical conversion test 4-1) Chemical conversion test a. Dimension of test piece 2-1) a. Same as b. Method of cleaning test piece 2-1) b. Same as c. Application of test oil 2-1) c. Same as d. Number of test pieces The number of test piece repetitions (n number) is 3. e. Preparation of Chemical Conversion Solution A standard solution was prepared using distilled water such that the chemical conversion agent PB3020 (manufactured by Parker Rising) meets the following conditions. Table 3 shows the standard solution preparation conditions.

[Table 3] f. Chemical Conversion Test Method The prepared chemical conversion solution was heated to a predetermined temperature, and the test piece was immersed in a chemical conversion treatment for a predetermined time. g. Judgment method After the operation, the test piece was dried immediately, the amount of the chemical conversion film attached on the surface of the test piece was measured, and the crystal state of the film was visually observed with a microscope. Table 4 shows the criteria.

[Table 4] As is clear from the results in Table 6, the composition of the present invention is superior to the comparative examples in lubricity, rust prevention and degreasing.

[Table 5]

[Table 6] (○; excellent △; acceptable ×; unacceptable) * ^{1 For the} coefficient of friction (μ), the above-mentioned sliding test was performed using the tool of FIG. 3 and a graph as shown in FIG. Are used as the values of P and D in equation (1), and μ is obtained according to equation (1). In order to raise the temperature to a predetermined temperature, a flexible heater was wrapped around the tool 1 and monitored with a CA thermocouple.

[0006]

[Effect] When the press-forming and rust-preventive oil of the present invention is used, in a press-forming process of a surface-treated steel sheet or the like, a single oil application as a rust-preventive oil to be shipped to a steel maker provides excellent press-forming workability and resistance. Oil stainability, rust prevention, and cleaning and degreasing in the pre-coating process can be achieved.

[Brief description of the drawings]

FIG. 1 is a diagram showing a mold (die and punch) in a deep drawing test.

FIG. 2 is a diagram showing a test piece holding wooden frame in an air exposure test which is one of the rust prevention evaluations.

FIG. 3 is a view showing the appearance of a sliding test tool.

FIG. 4 is an example of a diagram showing a load chart obtained by a sliding test.

[Explanation of symbols]

 Dd Die diameter Dp Punch diameter Db Specimen diameter H Wrinkle pressure P Press load rd Die shoulder radius rp Punch shoulder radius

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 125: 10) (C10M 163/00 137: 06 133: 44 159: 24 125: 10 129: 74) C10N 20:02 20: 06 30:00 30:06 30:12 40:24 (72) Inventor Hiroshi Hashimoto 1-chome, Mizushima-Kawasaki-dori, Kurashiki-shi, Okayama Pref. Kawasaki Steel Corporation Mizushima Works (72) Inventor Takaaki Hira Chiba 1 Kawasaki-cho, Chiba-shi Kawasaki Steel Corporation Research and Development Headquarters (56) References JP-A-51-14150 (JP, A) JP-A-58-132089 (JP, A) (58) Fields investigated (Int .Cl. ⁶ , DB name) C10M 163/00 C10M 137/06 C10M 133/44 C10M 159/24 C10M 125/10 C10M 129/74 C10N 20:02 C10N 20:06 C10N 30:00 C10N 30:06 C10N 30 : 12 C10N 40:24 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. A base oil comprising: 1 to 5 parts by weight of at least one kind of a pressability improving aid selected from the group consisting of (1) an alkali metal salt and an alkaline earth metal salt of an alkyl acid phosphate; 2) 0.1 to 1 part by weight of at least one oil stain inhibitor selected from the group consisting of alkylbenzotriazoles and arylbenzotriazoles; (3) alkali metal salts and alkaline earth metals of overbased alkylsulfonic acids 5 to 50 parts by weight of at least one rust-preventive additive selected from the group consisting of salts; (4) the group consisting of carbonates and oxides of alkali metals and alkaline earth metals whose main component is particles of 1 μm or less. And at least one solid lubricant selected from the group consisting of 1 to 10 parts by weight, and having a viscosity of 5 to 40 mm ² / sec.
A rust-preventive oil that is both press-worked and adjusted to (at 40 ° C.). 2. A base oil comprising: (1) 1 to 5 parts by weight of at least one pressability improving aid selected from the group consisting of alkali metal salts and alkaline earth metal salts of alkyl acid phosphates; 2) 0.1 to 1 part by weight of at least one oil stain inhibitor selected from the group consisting of alkylbenzotriazoles and arylbenzotriazoles; (3) alkali metal salts and alkaline earth metals of overbased alkylsulfonic acids 5 to 50 parts by weight of at least one rust-preventive additive selected from the group consisting of salts; (4) the group consisting of carbonates and oxides of alkali metals and alkaline earth metals whose main component is particles of 1 μm or less. 1 to 10 parts by weight of at least one solid lubricant selected from the group consisting of (5) (a) a saturated or unsaturated fatty acid having 12 or more carbon atoms, and (b) a fat Family polyol, depending from the group consisting of partial esters of barre was at least one oiliness improver 1-2
0 parts by weight, and a viscosity of 5 to 40 mm ² / s
ec (at 40 ° C.), a rust-preventive oil for both press working and press working.