JPH05339589A - Rustproofing press oil - Google Patents

Abstract

PURPOSE:To provide a rustproofing press oil having a viscosity of 20cSt or below, particularly 10cSt or below, and exhibiting high lubricating properties in pressing a galvnized sheet iron and to provide a rustproofing press oil which an give excellent lubricating properties, rustproofness, degreasability and capability of chemical conversion coating to a galvanized sheet iron. CONSTITUTION:The title oil comprises at least one member selected from the group consisting of sulfonates, at least one member selected from the group consisting of carboxylates, at least one member selected from the group consisting of a phosphoric ester derivative, a diester, a polyol ester, a fat and an oil, at least one member selected from the group consisting of overbased sulfonates and 1mum or smaller particles consisting mainly of potassium borate and a lowly viscous solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly used in the automobile industry and is in high demand from the viewpoint of rust prevention and corrosion prevention. The present invention relates to an anti-corrosion oil that can be used for press working of zinc plated steel sheets, which can be processed by a single lubricating oil.

In this case, the zinc plated steel sheet is a molten zinc plated steel sheet, an electric zinc plated steel sheet, a vapor deposited zinc plated steel sheet,
And alloyed zinc plated steel sheets obtained by alloying these, and all of the plated steel sheets containing zinc as a main component.

[0003]

2. Description of the Related Art The most important problem in terms of quality is the prevention of rusting during the work in process from the manufacture of zinc plated steel sheets by a steel manufacturer to the molding and processing of various parts by customers.

Therefore, in a normal zinc plated steel plate manufacturing process, a roll coating method, an oil dripping method is used immediately before winding on a coil or immediately before cutting into a sheet on the exit side of the final threading line (there are many zinc plating lines or recoiling). The appropriate amount of rust-preventive oil is applied by any method such as a coating method or an electrostatic coating method.

In general, rust preventive oils used for various kinds of steel sheets, especially Zn plated steel sheets, have less oil stains, do not corrode the Zn plated layer on the surface, have good degreasing property, good chemical conversion treatment property, and the like. From the standpoint of economical efficiency of reducing the carry-out amount, those having a viscosity at 40 ° C. of 20 cSt or less, preferably 5 to 10 cSt are used.

The steel sheet coated with rust preventive oil is strictly packed with volatile preventive paper, rust preventive paper laminated with polyethylene film, polyethylene film or the like and then shipped according to the delivery date.

The shipped coil or sheet is unpacked by the user and pressed into various product shapes.

The pressing process by the user is overhanging,
It is required that molding such as pulling and drawing is complicatedly combined with sliding applied with large and small surface pressures, and it is required that processing can be performed at the highest speed possible.However, as mentioned above, the oil film strength is weak due to the low viscosity, and it overhangs. Lubricity is insufficient to perform pulling, drawing, etc.

If the lubricity is insufficient in the press working of the zinc plated steel sheet, if the plated layer is the η phase of soft zinc, such as the electric zinc plated steel sheet and the molten zinc plated steel sheet, the η phase is the mold. So-called galling phenomenon occurs due to adhesion with the metal layer, and the plating layer is often peeled off, or in severe cases, plate rupture.

Further, for example, in the case of an alloyed molten zinc plated steel sheet produced by heat diffusion treatment after molten zinc plating, the plated layer is an iron / zinc alloy layer, but the relatively soft ζ phase on the plated surface. If (FeZn ₁₃ ) remains, a phenomenon similar to that of the fused zinc plated steel sheet may occur.

Not only the fracture but also the yield decrease,
The peeling of the plating layer also causes the product to be scratched by the peeling pieces, so that the yield is lowered or the efficiency is lowered due to an increase in the frequency of mold cleaning and the like.

Therefore, maintaining an appropriate lubrication state at the interface between the molding die and tool and the zinc plated steel plate is an important technical point.

[0013] For this reason, various techniques have hitherto been devised for the lubrication technique, but the most common one is a method of immediately applying a pressing oil which is a mixture of fats and oils and a mineral oil.

Since the press working oil to be used varies depending on the working degree, various viscosity grades (50 to 150 cSt, 40
C.), and a high-viscosity 70 to 80 cSt (40.degree. C.) is used for press working of the zinc plated steel sheet which is the subject of the present invention.

The most primitive method is hand coating lubrication, but in this case the productivity is low, and it is difficult to control the type, amount and position of the press working oil to be applied, resulting in variations in formability, There is a drawback that degreasing in the process is insufficient.

Therefore, in recent years, with the automation of the press work, the coating method has been changed to spray lubrication of the press working oil to the lubrication point, and improvement in productivity and control of the amount of oil coating can be seen. However, because of the high viscosity, the blanks are difficult to separate from each other, and two blanks may be pressed together, and equipment investment for oiling is required, and there are problems such as deterioration of the environment due to oil mist.

On the other hand, it is possible to use a high-viscosity press working oil as a rust preventive oil from a different viewpoint, but since it has a high viscosity, there is a limit to thin the oil film even if the coating method is taken into consideration. It is uneconomical because the loss due to

This problem can be solved if it is possible to reduce the viscosity of the currently used press working oil to the same level as the rust preventive oil, but in this case, lubricity is required in order not to hinder the working. The addition of extreme pressure additives is essential to raise the pressure.

When the extreme pressure additive is brought into contact with moisture in the air, hydrolysis, dehydrochlorination, etc. occur, and a corrosive substance is produced, so that the rust preventive performance is remarkably deteriorated. In addition, when a pressed product is welded, it not only causes rusting but also deteriorates the environment. It is difficult to suppress these phenomena with anticorrosive additives, and their practicality is particularly poor for zinc plated steel sheets.

That is, it has been impossible to satisfy the rust preventive property and the press processability with either the commercially available rust preventive oil or the press process oil with the present combination technology of additives.

Therefore, the inventors of the present invention have proposed a rust preventive oil for press working which is disclosed in JP-A-62-95396. The contents are (a) at least one selected from the group of sulfonates, (b) at least one selected from the group of carboxylates, (c) a phosphate ester derivative, a diester, a polyol ester, and a fat and oil. A rust preventive oil for press working, which comprises at least one kind selected from the group and (d) an alkali / alkaline earth metal salt of boric acid having particles of 0.1 μm or less as a main component. However, although the above invention can be applied to cold-rolled steel sheets whose surfaces are relatively inactive, it has been found that the rust preventive performance is insufficient in the case of zinc-plated steel sheets with active surfaces, and there is still room for improvement. I got it.

In order to solve these problems, there is little oil stain, the zinc plating layer on the surface of the steel sheet does not corrode, and a low viscosity rust preventive oil excellent in degreasing property and chemical conversion treatability is used for rust preventive treatment. It is important to keep the interface between the molding die and tool and the zinc plated steel sheet in a proper lubrication state when the press forming is performed with the oil film.

Taking these points into consideration, for the purpose of developing a press working rust preventive oil having a viscosity of 20 cSt or less and having a high lubricity at the time of press working of a zinc plated steel plate, the press working rust preventive oil for zinc steel plate is further used. (Japanese Patent Laid-Open No. 2-30
No. 5979). The content is selected from at least one selected from the group of (a) sulfonate, at least one selected from the group of (b) carboxylate, and from the group of (c) diesters, polyol esters, and fats and oils. At least one selected from the group of (d) superbasic sulfonate, and
(e) A rust preventive oil for zinc-plated steel sheets, which is also used for press working, containing particles of 1 μm or less containing potassium borate as a main component.

However, it is desirable to apply it as a rust preventive oil.
If a low-viscosity base oil necessary for obtaining a viscosity of 10 cSt or less (40 ° C.) is added, the oil film becomes thin and press workability deteriorates. If a high-viscosity base oil is added, it will be difficult to apply it as rust preventive oil, and the overlapping blanks will become difficult to separate during press working, resulting in a double blanking phenomenon, damaging the mold and reducing yield and productivity. There was a problem such as a decrease in Further, increasing the amount of lubricant to improve press workability is economically disadvantageous and there is still room for improvement.

[0025]

The object of the present invention is to determine the viscosity
It is an object of the present invention to provide a rust preventive oil for press working which has high lubricity at the time of press working of a zinc plated steel sheet at 20 cSt or less, particularly 10 cSt or less.

Another object of the present invention is to provide a press working rust preventive oil which has excellent lubricity, rust preventive property, degreasing property and chemical conversion treatability for zinc plated steel plates.

[0027]

The present invention provides (a) at least one member selected from the group of sulfonates, (b) at least one member selected from the group of carboxylates, and (c) phosphate ester. Derivatives, diesters, polyol esters, at least one selected from the group of fats and oils, (d) at least one selected from the group of superbasic sulfonates, and (e) potassium borate as a main component of 1 μm or less The present invention relates to (f) a rust preventive oil for press working of zinc plated steel sheet, which is characterized in that (f) a low-viscosity solvent is blended.

In the rust preventive oil for press working of the present invention, a base oil is blended in a base and diluted with a solvent to improve workability at the time of application, and an oil film at the time of pressing is controlled by adjusting the oil film thickness. The thickness can also be adjusted.

The action of each additive will be described in detail below.

First, sulfonates, carboxylates, and superbasic sulfonates are additives for the purpose of rust prevention.

Alkylbenzene sulfonates, alkylnaphthalene sulfonates, petroleum sulfonates and the like are used as sulfonates, and long-chain fatty acids such as stearic acid, naphthenic acid, oxidized wax and lanolin fatty acids are used as carboxylic acid salts. Examples thereof include salt.

The mechanism of action of the sulfonate salt is to form a protective film that prevents the permeation of water by its strong adsorption force to the metal surface, and the polar groups are oriented inward in the oil and the hydrocarbon groups are oriented outward. It prevents the contact of water with the surface of the zinc plating by forming a molecular assembly or micelle to solubilize the water.

Carboxylates have strong adsorptivity on metal surfaces,
It forms a protective film that prevents water permeation due to its adhesiveness and film forming property, and exerts a rust preventive effect.

Furthermore, the synergistic effect of using the sulfonate together with the sulfonate provides excellent rust-preventing properties, and also improves the solubility of the carboxylate itself in various solvents. The superbasic sulfonate is a plate in which the crystals of calcium carbonate in the dispersion contained therein have a flat plate shape, and when the film is formed, they are aligned to form a barrier and prevent the invasion of corrosive components. ..

Further, because of their alkalinity, they have a neutralizing effect on boric acid produced by the hydrolysis of potassium borate, and are essential especially for zinc plated steel sheets.

Examples of the super basic sulfonate include super basic calcium sulfonate, super basic barium sulfonate, super basic magnesium sulfonate, and the like.
Superbasic calcium sulfonate in which 90% calcium carbonate and 10 to 30% calcium hydroxide are dispersed in a colloidal form is preferable.

The concentrations of the above-mentioned three kinds of additives are not particularly limited, but 10% or less is sufficient for practical use, and 3 to 5% is preferable from the economical point of view.

Further, as the phosphoric acid ester derivative, a phosphoric acid ester amine salt, zinc dithiophosphate, molybdenum dithiophosphate, etc., as the diester, for example, dioctyl sebacate, dioctyl adipate, etc., and as the polyol ester, trimethylolpropane, pentaerythritol, Examples of the fats and oils include esters of triglyceride and the like and fatty acids having 10 to 18 carbon atoms, and vegetable fats and oils such as palm oil, rapeseed oil and castor oil, and animal fats and oils such as lard, lanolin and beef tallow.

These are intended to improve oiliness, and give a proper sliding action during press working and a good surface condition.

The concentration of the present additive is not particularly limited, but 20% or less is sufficient as the effect, and 10 to 15% is preferable from the economical viewpoint.

The boron compound of the present invention is a granular product obtained by reacting boric acid and potassium hydroxide in oil in the presence of a compound such as an alkali or alkaline earth metal sulfonate and a succinimide, which are generally referred to as detergent dispersants. A potassium borate dispersion having a particle size of 1 μm or less, preferably an average particle size of 0.1 μm is preferable.

The concentration of potassium borate is also not particularly limited, and 2% or less is sufficient for the effect, and 0.3 to 1% is preferable from the economical viewpoint. That is, from the viewpoint of lubricity, it is desirable that the concentration be high, but the effect of improving lubricity becomes small, which is economically disadvantageous. Further, since the dispersion stability in oil tends to deteriorate, the above range is desirable.

As such a potassium borate dispersion, for example, trade name "OLOA 9750" (Chevron Chemical
Company Oronite Additives Division) can be used.

The extreme pressure coating formed by the boron solid lubricant of the present invention is not due to a chemical reaction but to physical adsorption, and this adsorption film exhibits excellent lubricity especially in a high load region.

The reason for limiting the particle size to 1 micron or less is that when the solid lubricant is added to the rust preventive oil, the particle size is 1
This is because when the particle size exceeds micron, the dispersion stability in oil deteriorates due to the secondary aggregation. If the particle size exceeds 1 micron, the lubricant components will separate and settle during storage, causing insufficient lubrication, or the solid lubricant will become the core of rust formation when oiled on the metal surface, resulting in remarkable rust prevention. It may lead to lowering. Potassium borate with a particle size of 1 micron or less can be transparently dispersed in oil due to the synergistic effect of alkylbenzene sulfonate barium salt, super basic calcium sulfonate and lanolin fatty acid barium salt, and it is a great feature that there is no anxiety described above. ..

Further, as described above, potassium borate has a strong hydrophilicity and may be partially dissolved by contact with water to form boric acid. Since the generated boric acid component is corrosive to metals, it is necessary to take this measure when using it for rust preventive oil.

Since the anti-corrosion oil for press working of the present invention may absorb moisture in the use environment and may contain water in the process, it is possible to neutralize the boric acid produced by blending the above-mentioned super basic calcium sulfonate. It is also a feature that is done.

The solvent to be blended in the present invention is mainly a hydrocarbon type solvent which dissolves the base oil described below and the above additives,
For example, hydrogenated kerosene, normal paraffin, isoparaffin, naphthene-based solvent and the like can be used, and those which are naturally dried after being applied to a zinc plated steel plate can be used. Flash point is 70 ℃
Less than and above are included, but those with a flash point of 70 ° C or higher are desirable in terms of work environment and fire hazard prevention. In order to improve the pressability at the time of press working, the viscosity of the oil film remaining at the time of press working is high, and it is more preferable that there are more fine particles in the oil film, but by blending these solvents, the lubricating additive in the oil agent In addition to being able to reduce the concentration, the addition of a high-viscosity base oil described below can also contribute to improving the dispersion stability of the particles.

After the above-mentioned solvent is dried, it remains as an oil film on the zinc plated steel sheet, and a mineral oil having various viscosities or synthetic oils is used as a base oil for imparting rust resistance until processing and lubricity at the time of pressing. Oil can be used and is not particularly limited. A base oil having a high viscosity is desirable in order to enhance the lubricity during press working, but it is necessary to maintain the viscosity of the oil agent and the oil film thickness appropriately.

In the present invention, the mixing ratio of the components (a) to (e) is
Component (a) is 10% by weight or less, preferably 3 to 5% by weight, (b)
Component is 10% by weight or less, preferably 3 to 5% by weight, component (c) is 20% by weight or less, preferably 10 to 15% by weight, component (d) is 10% by weight or less, preferably 3 to 5% by weight The amount of the component (e) is 2% by weight or less, preferably 0.3 to 1% by weight, and a base oil and a solvent which can be adjusted to have an appropriate viscosity are added thereto.

The rust preventive oil for press working of zinc plated steel sheet of the present invention can be easily produced by a conventional method.
That is, a predetermined amount of a base oil is added with a predetermined amount of a rust preventive additive, a lubricating additive, and a solid lubricant, and the mixture is stirred and mixed. For the mixing, a conventional mixing tank with a stirrer can be used, and usually 60 to 100
It is carried out at 0 ° C., and a time of 1-2 hours is sufficient. afterwards,
Preferably, after cooling to 50 ° C. or lower, a predetermined amount of solvent is gradually added, stirred and mixed.

Thus, by combining the components of the above-mentioned composition, as will be demonstrated in the examples described below, a rust preventive oil for press working which has excellent rust preventiveness and pressability for zinc plated steel sheets. Is obtained.

[0053]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. Nos. 1 to 3 are examples, and Nos. 4 to 6 are comparative examples. The results are shown in Table 1. In the table, the carbon number of the alkyl moiety of the alkylbenzene sulfonic acid is 13-18, and the carbon number of the fatty acid part of the lanolin fatty acid is 11-19.

The test methods and evaluation criteria for rust prevention, lubricity, degreasing and chemical conversion treatment are as follows.

Anticorrosion property: Test zinc plated steel plate a) Molten zinc plated steel plate (plating amount 90 g / m ² ) b) Alloyed molten zinc plating plate (plating amount 60 g / m ² ) Evaluation method Above zinc plated steel plate Is immersed in the product of the present invention and comparative oil,
It was left to stand for 60 days in a thermo-hygrostat at 49 ° C. and 95% RH, and the corrosion state of the plating layer was visually evaluated. ○: There is no corrosion. Δ: Discoloration due to corrosion is recognized. ×: Discoloration due to corrosion is remarkable.

Lubricity: Tested zinc plated steel sheet Alloyed molten zinc plated steel sheet (plating amount 60 g / m ² ) Evaluation method About 1 g / g of alloyed molten zinc plated steel sheet in which the product of the present invention and comparative oil were sampled from the same coil Among the loads (every 25 kgf) applied to the bead mold when it was applied by m ² and passed through the bead mold and pulled out, the load immediately before the zinc plated steel plate was broken (breaking limit load Pc, kgf) was evaluated. In addition, No.
Tests 1 to 3 were conducted after aging at 25 ° C. for 3 weeks. The larger the breaking limit load, the better the lubricity. Sample shape: 17 x 400 x 0.7 mm (width x length x thickness) Extraction speed: 500 mm / min. Stroke: 200mm

Degreasing property: Test zinc plated steel sheet Alloyed molten zinc plated steel sheet (plating amount 60g / m ² ) Evaluation method Degreasing was carried out for 20 seconds by a spray method using a carbonic acid soda-based degreasing agent, and wetting with water after washing The area ratio (%) was evaluated. The higher the wetted area ratio, the better the degreasing property.

Chemical conversion treatability: Tested zinc plated steel sheet Alloyed fused zinc plated steel sheet (plated coating amount 60 g / m ² ) Evaluation method Chemical conversion treatment was performed by a dipping method using a zinc phosphate-based chemical conversion treatment liquid, and the deposited amount, The crystal form was evaluated. ○: Dense crystals ×: Coarse crystals

Regarding the lubricity, degreasing property, and chemical conversion treatability, about 1 g / m ^{2 of} oil was applied to the alloyed molten zinc plated steel sheet, and a constant temperature and humidity chamber (55 ° C., 60% RH) was applied prior to evaluation. ) In 7
It was aged for a day.

As shown in Table 1, the product of the present invention is excellent in rust prevention and lubricity, and has no problem in degreasing property and chemical conversion treatment.
It can be seen that it has excellent performance as a rust preventive oil that is also used for press working for zinc plated steel sheets.

[0061]

[Table 1]

[0062]

【The invention's effect】

1. Pressing oil and processing oil coating equipment are not required, and significant cost savings can be achieved. 2. Since the pressing oil application process can be omitted, the handling time can be shortened and productivity can be improved. 3. Factory pollution due to scattering and leakage of press oil will be eliminated, and environmental improvement will be possible. 4. It is possible to prevent breakage of the zinc plated steel sheet during press forming, peeling of the zinc plating, etc., and contribute to improvement in yield and productivity. 5. The blanks are released more easily during press working, and double blanking is eliminated, improving the yield. 6. The low viscosity makes it easier to control the amount of oil applied and saves the amount used. 7. The oil that oozes out from the plates and coils is reduced, which contributes to the beautification of the environment. 8. Since the formability is improved, it is not necessary to use expensive high quality zinc plated steel plate or alloyed plated steel plate, and it is possible to easily form with a cheaper material.

As described above, by using the rust preventive oil for press working of the present invention, a great deal of merit is provided in the rust preventive oil applying step and the press step, and a great industrial effect is brought about.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 129: 26 137: 10 129: 74 159: 08 125: 26 129: 52 159: 24) C10N 10 : 02 10:04 20:06 Z 8217-4H 30:06 30:12 40:24 (72) Inventor Tamio Akada 14 Meguro-cho, Mikage-cho, Higashinada-ku, Hyogo, Hyogo Prefecture (72) Inventor Michihiro Yamamoto Suita, Osaka 13-3 Fujigaoka Town

Claims (1)

[Claims] 1. An (a) at least one member selected from the group of sulfonates, (b) at least one member selected from the group of carboxylates, (c) a phosphoric acid ester derivative, a diester, a polyol ester, At least one selected from the group of fats and oils
Seed, (d) at least one member selected from the group of superbasic sulfonates, and (e) 1 μm containing potassium borate as a main component
An anti-corrosion oil for zinc press steel sheets which is used for press working, characterized in that it contains particles of m or less and (f) is mixed with a low-viscosity solvent.