JPH0244878B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention combines rust prevention treatment during the storage period of various steel sheets, especially thin steel sheets, and press processing when processing the steel sheets, which are mainly used in the automobile industry and home appliance industry. This invention relates to a rust preventive oil that can be used for press processing and which can be treated with a lubricating oil. (Prior art) The most important quality issue during the manufacturing process from the time a thin steel sheet is manufactured at a steel manufacturer to the time it is molded and processed into automobiles and home appliances by the customer is prevention of rust. For this reason, in the normal manufacturing process of thin steel sheets, coating roll method, oil dripping method, static Apply an appropriate amount of anti-rust oil depending on the purpose and use using one of the methods such as electric coating. The first requirement for a rust preventive oil is to be able to completely prevent rust from forming on the steel sheet immediately before use, but it is also a prerequisite that the oil can be sufficiently degreased in the degreasing process before chemical conversion treatment at the time of use. Steel plates coated with the most suitable anti-corrosion oil are tightly packed with evaporative anti-rust paper, anti-rust paper laminated with polyethylene film, or polyethylene film, and stored in a warehouse until shipped. The shipped coil or sheet is pressed into a product shape by the user. Actual press working involves a complex combination of simple forming processes such as stretching, pulling, and drawing, and requires processing to be performed at the highest possible speed. For this reason, it is necessary to design the steel plate material according to the shape, and it is an important technical point to maintain an appropriate lubrication state at the interface between the molding die, tool, and steel plate. Press cracks, scratches, wrinkles, etc. occur on the steel plate side due to insufficient lubrication, and scratches occur on processing jigs. If excessive, it may cause damage to the tool. Alternatively, abrasion powder generated when the die bites the surface of the steel plate may accumulate, causing concave scratches on the steel plate. Furthermore, even if the lack of lubrication is mild, the machining speed must be reduced in order to prevent the occurrence of the various defects described above. Various approaches to this lubrication technology have been made in the past, but the most common one is wet lubrication, in which a mixture of oils and mineral oil is immediately applied.
In recent years, with the rationalization of press work through mechanization, there has been a shift to spray lubrication of press processing oil to the lubricated parts, but it is necessary to select various lubricants depending on the type of processing material, mold, tool, etc. It is difficult to control the amount of application, and there is a lot of waste due to taking it out.
It faces problems such as a poor environment. Solving these various problems and streamlining processes will be a great benefit for the steel and automobile industries, and using a single lubricant for rust prevention and press processing is an important issue. It was hot. In general, anti-corrosion oils used for various types of steel sheets, especially thin steel sheets, have low viscosity (40°C , 20 cst or less) are used. However, since the viscosity is low, the oil film strength is also weak, and the lubricity is insufficient for stretching, pulling, drawing, etc. On the other hand, since the press processing oil used differs depending on the degree of processing, various viscosity grades (50 to
150cst (40℃), and those with a viscosity of 7 to 80cst (40℃) are used for press working of thin steel sheets. When such a highly viscous press working oil is used as a rust preventive oil, there is a limit to how thin the oil film can be made even if the application method is considered, and it is uneconomical because there is a large loss due to carry-out. However, this problem could be solved if it were possible to lower the viscosity of the currently used press working oil to the same level as rust preventive oil. Addition of extreme pressure additives is essential. When extreme pressure additives come into contact with moisture in the air,
Hydrolysis, dehydrochlorination, etc. occur and corrosive substances are generated, resulting in a significant decrease in rust prevention performance. This phenomenon is difficult to suppress with anti-rust additives.
It has little practicality. In other words, with the current combination technology of additives, it is impossible to satisfy both rust prevention properties and press workability using either commercially available rust preventive oils or press working oils. (Problems to be Solved by the Invention) An object of the present invention is to provide a rust-preventing oil for both press working and having the functions of both a rust-preventing oil and a press working oil. (Means for Solving the Problems) The present invention provides (a) at least one member selected from the group of sulfonic acid salts, (b) at least one member selected from the group of carboxylic acid salts, and (c) phosphoric acid salts. It is characterized by containing at least one member selected from the group of ester derivatives, diesters, polyol esters, oils and fats, and (d) an alkali/alkaline earth metal salt of boric acid whose main component is particles of _0.1 μm or less. Concerning anti-corrosion oil for press processing. If rust prevention oil is applied during the steel sheet manufacturing process to temporarily prevent rust during the storage period, and the customer can press the steel sheet in that state, the press processing process can be simplified and the process can be completed in one step. This enables significant rationalization. Such lubricants offer a number of benefits, including: 1. Press processing oil and processing oil spray equipment are no longer required, resulting in significant cost savings. 2. Since the pressing process can be omitted, handling time can be shortened, leading to improved productivity. 3. Factory pollution caused by splashing and leakage of press processing oil will be eliminated, making it possible to improve the environment. Furthermore, molded products are degreased and cleaned after being coated with press oil, but even when processing with a single lubricant, there is no need to install new post-processing equipment, and existing degreasing equipment can be used as is. can. In the present invention, examples of sulfonates include alkylbenzenesulfonates, alkylnaphthalenesulfonates, petroleum sulfonates, etc., and examples of carboxylates include long-chain fatty acids such as stearic acid, naphthenic acid, oxidized wax, and lanolin fatty acids. Examples include salt. In addition, phosphoric acid ester derivatives include phosphoric acid ester amine salts, zinc dithiophosphate, molybdenum dithiophosphate, etc., diesters include dioctyl sebacate, dioctyl adipate, etc., and polyol esters include trimethylolpropane, pentaerythritol, triglyceride, etc. Examples of fats and oils include vegetable oils such as palm oil, rapeseed oil, and castor oil, and animal fats and oils such as lard and lanolin tallow. The boron compound used in the present invention is an alkali/alkaline earth metal salt of boric acid, and preferably has a particle size of 0.1 μm or less as a main component. When a fixed lubricant is added to a rust preventive oil, the dispersion stability in the oil may deteriorate depending on the particle size and secondary aggregation. This may cause the lubricant components to separate and settle during storage, causing insufficient lubrication, or when the lubricant is applied to metal surfaces, the fixed lubricant may become the core of rust formation, leading to a significant drop in rust prevention properties. . A major feature of the boron compound used in the present invention is that it can be transparently dispersed in oil due to the synergistic effect of the sulfonic acid salt and the carboxylic acid salt, and is free from the above-mentioned concerns. The film formed in the case of the boron-based solid lubricant of the present invention is not caused by a chemical reaction but by physical adsorption, and this adsorbed film is an additive that has excellent lubricity and does not have antirust properties. The present inventors found out. In the present invention, the blending ratio of components (a) to (d) is (a) component
25 to 75 parts (by weight, the same applies hereinafter), preferably 45 to 75 parts
55 parts, (b) component 25-75 parts, preferably 45-55 parts, (c)
The amount of component (d) is preferably 1 to 100 parts, preferably 5 to 50 parts, and 1 to 15 parts, preferably 8 to 12 parts of component (d).
It is preferable to mix 840 to 885 parts of base oil such as machine oil to this. (Example) Examples and comparative examples will be described below. Example 1 A rust preventive oil for press processing was prepared with the following composition.
This is called mixed oil A. Barium salt of alkylbenzenesulfonate (alkyl moiety has 13 to 18 carbon atoms)
After heating and mixing 50 g of lanolin fatty acid barium salt (fatty acid having 11 to 29 carbon atoms) and 50 g of trimethylolpropane oleyl ester at 80°C for 30 minutes, the mixture was cooled to 60°C. Then borate potassium salt 10
g and machine oil (ISO VG10) 840ml, 60
The mixture was heated and mixed at ℃ for 1 hour to obtain 1006 ml of a reddish-brown transparent liquid. The evaluation results of the rust prevention, lubricity, and degreasing properties of Mixed Oil A are shown in Tables 1 and 2. Very good results were obtained in terms of rust prevention, lubricity, and degreasing properties. Example 2 A rust preventive oil for press processing was prepared with the following composition.
This is called mixed oil B. Alkylbenzenesulfonic acid barium salt 50g, lanolin fatty acid barium salt
After heating and mixing 50g of palm oil and 50g of palm oil at 80℃ for 30 minutes, the mixture was cooled to 60℃. Then borate potassium salt
Add 10g and 840ml of machine oil (IS0 VG10),
Heat and mix at 60℃ for 1 hour to obtain 1006ml of reddish-brown transparent liquid.
I got it. The evaluation results of the rust prevention, lubricity, and degreasing properties of Mixed Oil B are shown in Tables 1 and 2. Here, palm oil, which is a natural oil, was used instead of trimethylolpropane oleyl ester, which was used as the oily agent in Example 1. Rust prevention, lubricity, and degreasing properties equivalent to Mixed Oil A were confirmed. Example 3 A rust preventive oil for press processing was prepared with the following composition.
This is called mixed oil C. Alkylbenzenesulfonic acid barium salt 50g, lanolin fatty acid barium salt
After heating and mixing 50 g of acidic phosphate ester amine salt (ester moiety having 4 to 6 carbon atoms) for 30 minutes at 80°C, the mixture was cooled to 60°C. Next, 10 g of potassium borate salt and 885 ml of machine oil (IS0 VG10) were added, heated and mixed at 60℃ for 1 hour, and a reddish-brown transparent liquid was produced.
Obtained 1005ml. Tables 1 and 2 show the evaluation results of the rust prevention, lubricity, and degreasing properties of Mixed Oil C. Here, instead of the trimethylolpropane oleyl ester used as the oily agent in Example 1, an acidic phosphate ester amine salt was used. In order to provide lubricity with acidic phosphoric acid ester amine salt alone, it is necessary to add 2wt/vol% or more, but the rust prevention properties are significantly reduced due to hydrolysis. In this example, the effect of the boron compound is 0.5wt/vol.
%, no adverse effects were observed, and the same rust prevention, lubricity, and degreasing properties as Mixed Oil A were confirmed. Example 4 A rust preventive oil for press processing was prepared with the following composition.
This is called mixed oil D. Alkylbenzenesulfonic acid barium salt 50g, lanolin fatty acid barium salt
After heating and mixing 50 g of zinc dithiophosphate and 5 g of zinc dithiophosphate at 80°C for 30 minutes, the mixture was cooled to 60°C. Next, 10 g of potassium borate salt and 885 ml of machine oil (IS0 VG10)
was added and mixed under heating at 60°C for 1 hour to obtain 1005 ml of a reddish-brown transparent liquid. The evaluation results of the rust prevention, lubricity, and degreasing properties of Mixed Oil D are shown in Tables 1 and 2. In this example, rust prevention, lubricity, and degreasing properties equivalent to Mixed Oil C were confirmed. Example 5 A rust preventive oil for press processing was prepared with the following composition.
This is called mixed oil E. Alkylbenzenesulfonic acid barium salt 50g, lanolin fatty acid barium salt
50g, trimethylolpropane oleyl ester
45g, acidic phosphate ester amine salt 5g at 80℃
After heating and mixing for 30 minutes, cool to 60°C. Next, add 10 g of potassium borate salt and machine oil (IS0
Add 840ml of VG10), heat mix at 60℃ for 1 hour,
1006 ml of a reddish-brown transparent liquid was obtained. The evaluation results of the rust prevention, lubricity, and degreasing properties of mixed oil E are shown in Tables 1 and 2.
Shown in the table. In this example, rust prevention, lubricity, and degreasing properties equivalent to Mixed Oil C were confirmed. Comparative Example 1 A comparative oil having the following composition was prepared. Compare this with oil F
shall be. Alkylbenzenesulfonic acid barium salt
After heating and mixing 50 g of lanolin fatty acid barium salt, 45 g of trimethylolpropane oleyl ester, and 5 g of acidic phosphoric acid ester amine salt at 80℃ for 30 minutes, add 850 ml of machine oil (IS0 VG10).
Heat and mix at 60℃ for 1 hour to obtain 1006ml of reddish-brown transparent liquid.
I got it. The evaluation results of the rust prevention, lubricity, and degreasing properties of Comparative Oil F are shown in Tables 1 and 2. In this example, each performance was evaluated when no boron compound was added. Although the rust prevention and degreasing properties were the same as those of mixed oils A to E, the lubricity required for press working was not obtained, confirming the effect of the boron compound. Comparative Example 2 Comparative oil G is a typical rust preventive oil that is currently used in large quantities for the rust preventive treatment of thin steel plates in the steel industry (viscosity: 40°C; 6.35 cst, specific gravity: 15/4°C; 0.876, flash point:
124℃). Tables 1 and 2 show the evaluation results of the rust prevention, lubricity, and degreasing properties of Comparative Oil G. Regarding rust prevention and degreasing properties, the performance was almost the same as that of mixed oils A to E, but the lubricity was such that it could not be used at all as a press working oil. Comparative Example 3 Comparative oil
(viscosity 40℃; 77.8cst, specific gravity 15/4℃;
0.922, flash point 226℃). The evaluation results of the rust prevention, lubricity, and degreasing properties of Comparative Oil H are shown in Tables 1 and 2. Although the lubricity and degreasing properties were close to those of mixed oils A to E, the rust prevention properties were completely unusable. From the results shown in Tables 1 and 2, it is clear that the lubricating oil composition of the present invention has sufficient performance as a rust preventive oil for press processing. Comparative Example 4 A rust preventive oil for press processing was prepared with the following composition.
This is designated as Comparative Oil I. Alkylbenzenesulfonic acid barium salt 50g, lanolin fatty acid barium salt
50g, trimethylolpropane oleyl ester
45g, acidic phosphate ester amine salt 5g at 80℃
After heating and mixing for 30 minutes, cool to 60°C. Next, 10 g of a potassium borate salt mainly composed of particles of 1 μm and 840 ml of machine oil (ISO VG10) prepared separately from the potassium borate salt mainly composed of particles of 0.1 μm or less used in Examples 1 to 5. was added and heated and mixed at 60°C for 1 hour to obtain 1006 ml of a reddish-brown transparent liquid. The first evaluation results of the rust prevention, lubricity, and degreasing properties of Comparative Oil I
Shown in Table and Table 2. In this example, we confirmed the relationship between the particle size of potassium borate salt used as a rust preventive oil for press processing, rust preventive properties, and lubricity. If the particle size was 1μ, the malleability, which is important for press working, would be compromised, and the oil could not be used as a press working oil at all.

【table】

【table】

[Table] Description of test method Rust prevention test 1 Wet test 1,1 Apparatus Consists of a test piece stand, water tank, air supply device, flow meter, etc. (JIS K 2246) 1, 2 Test piece Cold rolled steel plate 60 x 80 x 1.0~2.0mm 1, 3 Conditions a Temperature at test piece hanging position 49±1°C b Relative humidity 95% or more c Air flow rate Humidity box contents Approximately 3 times the product/h 1.4 Judgment Measure the degree of rust occurrence after 720 hours. A class 0%, B class 1-10%, C class 11-25%, D class 26-50%, E class 50% or more 2 Normal stack 2.1 Preparation of test piece SPC dull steel plate (100 x 200 x 0.7 mm) after dry-wiping the alkaline cleaner (Rd-75, 20g/
, 60℃, 60 seconds spray), then rinse with water and dry. 2.2 Skin pass agent, anti-rust oil treatment Immediately squeeze with a rubber roll after immersing in a 5-10% aqueous solution of skin pass agent. Next, apply rust preventive oil using a roll coating method. Stacking 2 and 3 Stack each set of 10 sheets, wrap them in paper and tighten with bolts to a torque of 30 kg/cm ² . 2,4 Acceleration test Constant temperature and humidity chamber (temperature 50±1℃, relative humidity 90~
95%) for 30 and 60 days. 2.5 Judgment After the test, observe the occurrence of rust, oil stains, etc. on the overlapping surfaces of the test pieces. ○; No rust or oil stains ×; Yes 3 V stack 3.1 Preparation of test piece Preparation is performed in exactly the same manner as in 2.1. 3.2 Skin pass agent, anti-corrosion oil treatment Prepared in exactly the same manner as in 2.2. 3.3 Stacking A set of 5 oiled plates is stacked using spacers, wrapped in paper, and then bolted to 30kg/
Tighten with a torque of cm ² . 3,4 Acceleration test Constant temperature and humidity chamber (temperature 60±1℃, relative humidity 85
%) for 21 and 35 days. 3, 5 Judgment Perform the judgment in exactly the same way as 2, 5. 4 Degreasing properties 4.1 Preparation of test pieces Stack 10 pieces in exactly the same way as the normal stack in 2, and place them in a constant temperature and humidity chamber (temperature 50℃, relative humidity).
90-95%) stored for 30 days. 4.2 Test method Spray degreasing using alkaline cleaner (Rd75) under the following conditions. Concentration: 10g/Temperature: 50~55℃ Time: 10 seconds, 30 seconds, 60 seconds Spray device: Spray pressure 0.7Kg/ ^cm2 , spray distance 30cm, nozzle diameter 2mm, number of nozzles 14 on each side 4,3 Judgment After degreasing, rinse with water for 30 seconds and stand at 60℃.
After 20 to 30 seconds, the water-wetted area (%) is visually determined. 5 Four-ball test 5,1 type Four-ball lubrication tester (Soda type) 5,2 Test steel balls Steel balls for ball bearings 3/4″ (19.05mm) JIS B 1501 5,3 Vertical rotation speed 220 rpm 5,4 Liquid Volume, temperature 50ml, room temperature 5.5 Pressure accumulator load 1-10Kg/cm ² 5.6 Measurement a. Set 3 steel balls in the sample oil container and 1 steel ball on the vertical shaft. b. Place the sample oil in the container. c. Apply a load to the steel ball. (0.5Kg/min) d. Rotate the vertical shaft, perform the operation in c continuously, and record the load-bearing pressure (seizure pressure 0.5Kg/cm ² ). 6. Four-ball test 6,1 Type Four-ball lubrication tester (Soda type) 6,2 Steel balls for testing Steel balls for ball bearings 3/4″ (19.05mm) JIS B 1501 6,3 Vertical shaft rotation speed 4 rpm 6,4 Liquid volume, temperature 50 ml, room temperature 6.5 Pressure accumulator load 1-10 Kg/cm ² 6.6 Measurement a. Set one steel ball on the vertical axis of three steel balls in the sample oil container. b Put the sample oil into a container. (50ml) c Apply a load to the steel ball. (1 to 10Kg, 0.5Kg/min) d Rotate the vertical axis. (60 seconds) e Continuously record the torsion angle of the torsion rod with an indicator. f Change the load on the steel ball and repeat steps d and e. 6, 7 Records a Load pressure Kg/cm ² (Seizing pressure 0.5Kg/cm ² ) b Friction coefficient μ Determined from load and torsion angle. Total load P=π/d×D ² P−8.6 D: Cylinder diameter (8cm), P: Hydraulic pressure (Kg/cm ² ), 8.6: Accessory weight (Kg) Vertical load per unit ball Frictional force per unit ball μ=f/ω f=T/1.65 T: Frictional moment (determined from the torsion moment to torsion angle curve) 7 Cylindrical extension test 7.1 Testing machine TF-102-30 type (manufactured by Tokyo Hoshiki) 7.2 Test ability Capacity Punch force max 30Ton Wrinkle holding force max 6Ton Stroke Punch max130mm Wrinkle holding max 5mm Punch rising speed max200mm/min 7.3 Test conditions a Punch φ60.0−6R b Beaded die φ62.0− 6R c Wrinkle holding force 5Ton d Punch speed 5~20mm/min 7.4 test a Test material 0.75mmSPC b Size 150×150mm c Single side application of test oil (1.5~2.0g/m ² ) d Deep drawing tester Set the sample (on the oiled side of the punch). e. Wrinkle holding force setting: 5Ton. f. Punch speed: Push out at 5 to 2 mm/min. g. Measure the overhang height when cracks appear. 8 Cylindrical drawing test 8.1 Test machine Same as cylinder overhang 8.2 Test capacity 〃 8.3 Test conditions a Punch φ60.0-6R b Die φ62.0-6R c Wrinkle holding force 0.3-5Ton d Punch speed 200mm/ min 8,4 test a Test material 0.75mmSPC b Blank size φ110 to φ130 5m interval (press punching) c Apply test oil to one side (1.5 to 2.0 g/m ² ) d Set sample on deep drawing test machine (coating) (Oil surface die side) e Set wrinkle presser pressure (0.3 to 5Ton) f Squeeze at punch speed 200mm/ming Evaluation 〇: No cracks or wrinkles ×: Cracks or wrinkles occur

Claims (1)

[Claims] 1 (a) at least one selected from the group of sulfonates consisting of alkylbenzene sulfonates, alkylnaphthalene sulfonates, and petroleum sulfonates; (b) consisting of stearic acid, naphthenic acid, oxidized wax, and lanolin fatty acids; At least one member selected from the group of carboxylic acid salts, (c) phosphate ester amine salt, zinc dithiophosphate, molybdenum dithiophosphate, dioctyl sebacate, dioctyl adipate, trimethylolpropane, pentaerythritol, triglyceride having 10 or more carbon atoms; (d) lithium and potassium boric acid whose main component is particles of 0.1 μ or less; sodium,
A rust preventive oil for press processing, characterized by containing at least one selected from the group of calcium, magnesium and barium salts.