JPH108077A - Lubricant for metal plastic working - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject lubricant to be used in metal calendering, pressing, drawing forming, etc., excellent in lubricity and stock liquor stability, containing a polycondensate of ricinoleic acid or the like and/or an ester obtained from this polycondensate and an aliphatic alcohol or acid. SOLUTION: This lubricant contains (A) a polycondensate of ricinoleic acid or hydroxystearic acid and/or (B) an ester from this polycondensate and a 12-22C aliphatic carboxylic acid or a 12-22C aliphatic alcohol. The acid values of the ingredients A and B are pref. 20-160 (esp. 30-150)mgKOH/g, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating oil used in plastic working of metals such as iron, steel, aluminum and stainless steel, for example, in rolling, pressing, drawing and forming. More specifically, an object of the present invention is to provide a lubricating oil agent having excellent lubricating properties and stock solution stability.

[0002]

2. Description of the Related Art Conventionally, lubricating oils for metal plastic working have been based on animal and vegetable oils and fats such as mineral oil, beef tallow, palm oil, lard, etc., or fatty acid esters as base oils, and saturated fatty acids such as stearic acid and oleic acid. Unsaturated fatty acids or dibasic acids such as dimer acid are added as oiliness improvers, and further, rust preventive additives, extreme pressure additives, antioxidants and the like have been used.

Here, in the case of a cold rolling oil or a roll forming oil in which importance is attached to cooling of heat generated during plastic working,
A nonionic, cationic, anionic or amphoteric surfactant is further added to the above composition, and when used in practice, it has been diluted with water and used as an emulsion.

[0004] An oiliness improver is added to reduce the load during plastic working, to prevent work surface precision, or to prevent seizures or the like caused by insufficient lubrication. Among the conventional ones, dibasic acids such as dimer acid show particularly excellent effects.

[0005] However, a lubricant containing dimer acid is excellent in lubricity, but has a drawback that a viscous film is formed on the surface of a plastically processed product and a mechanical device used for the plastic working, thereby causing adhesion stains.

[0006] Saturated fatty acids such as stearic acid, which are widely used, are relatively excellent in deteriorating property and lubricity, but have a high melting point and are subjected to liquid phase separation during storage of oils, and to plastically processed products. There is a lot of dirt on the surface.

Unsaturated fatty acids such as oleic acid have a relatively low melting point and are liquid at room temperature (25 ° C.), so that the liquid stability during storage of the oil agent is excellent, but the deterioration due to the unsaturated bond is caused. And stains due to the degradation products are generated.

Further, when diluted with water and used as an emulsion, iron powder generated during plastic working such as rolling, roll forming, pressing and drawing is mixed into the emulsion to make the emulsion emulsified. , And separates and floats to form scum, which causes contamination.

[0009] In recent years, cold rolling oil, which is one of the lubricating oils for plastic working, has been used as a cationic surfactant for the purpose of stabilizing the emulsifying dispersibility and cleaning the rolling mill itself or around the machine. It has become In order to increase the cationicity of the cationic surfactant, a fatty acid or phosphoric acid is added as a counter ion, so that the emulsifying dispersibility is greatly changed with time, foaming is frequent, and stable lubricity is obtained. In the worst case, processing may not be possible.

[0010] In addition, rust is liable to be produced from the materials to be rolled, such as ordinary steel, silicon steel and high carbon steel, and the cold rolling oil used in cold rolling is triethanol as an antirust additive. A fatty acid salt of an alkanolamine such as an amine, diethanolamine, or monoethanolamine is added. In this case, the emulsifying dispersibility greatly changes over time, and problems such as generation of emulsified scum and foaming frequently occur.

Further, as a roll forming oil such as roll forming, a soluble type oil having extremely excellent emulsification and dispersion stability is used, but a relatively large amount of alkanolamine fatty acid salt is added for rust prevention. The same problem as the cold rolling oil occurs.

[0012]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and is excellent in low melting point, lubricity, deterioration resistance, liquid stability during storage, and when diluted with water to obtain an emulsion. To provide a lubricating oil for metal plastic working which is excellent in emulsification stability when formed into a solution and has no problems such as foaming when used in circulation, and which does not cause adhered stains on plastic processed products and mechanical devices. It is an object.

[0013]

As a result, (i) a polycondensate of ricinoleic acid or hydroxystearic acid;
Esters of the polycondensate with an aliphatic carboxylic acid having 12 to 22 carbon atoms or an aliphatic alcohol having 12 to 22 carbon atoms,
The present inventors have found that a lubricating oil for plastic working containing at least one of the above-mentioned objects can solve all the above-mentioned problems, and have completed the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Here, a polycondensate of ricinoleic acid or hydroxystearic acid, or a polycondensate thereof and a polycondensate of 1 carbon atom
The acid value of each of the ester with an aliphatic carboxylic acid having 2 to 22 or an aliphatic alcohol having 12 to 22 carbon atoms is 20 to 1
60 mgKOH / g, preferably 30 to 150 mgKOH
/ G is required. If the acid value is less than 20, the emulsifiability and lubricity are poor, and if it is higher than 160, the molecular weight of the polycondensate decreases and the lubricity decreases, which is not preferred.

The amount of the polycondensate or the ester of the polycondensate added to the lubricating oil for metal plastic working may be within the range of oiliness improvers conventionally added, such as fatty acids, animal and vegetable oils and fats, esters and the like. 0.5 to 60% by weight based on the base oil
Is added.

The production method of the polycondensate of ricinoleic acid or hydroxystearic acid is not limited at all. For example, the polycondensate is heated to 180 to 220 ° C. in a nitrogen stream to have an acid value of 20 to 1
When the reaction is completed at the time when the concentration reaches 60 mgKOH / g,
The expected product is obtained.

Further, the esterification reaction of the polycondensate is carried out, for example, at 160 to 220 ° C. in the presence of a catalyst such as paratoluenesulfonic acid (PTS), sulfuric acid, hydrochloric acid, phosphoric acid, sodium methylate, zinc chloride or the like. The heating reaction may be performed in an inert gas atmosphere, and the reaction may be terminated when the acid value reaches 20 to 160.

In the present invention, ricinoleic acid or hydroxystearic acid is intermolecularly condensed by a heat reaction to form a dimer, trimer or tetramer. The reaction at this time is mainly an intermolecular condensation reaction, and the polymerization reaction due to the double bond is extremely small. The reason can be seen from the lack of iodine reduction in the product.

In the present invention, the ester of the above polycondensate with a carboxylic acid or an alcohol may be a polycondensate
For alcohols and polycondensates-fatty acids.

Since the polycondensate of ricinoleic acid or hydroxystearic acid is an intermolecular condensate, the above ester is formed by esterification with an OH group or COOH group remaining in the intermolecular condensate with an alcohol or carboxylic acid. .

The following can be exemplified as the alcohol that can be used at this time. A saturated or unsaturated alcohol having 12 to 18 carbon atoms, preferably 16 to 18 carbon atoms
Is a saturated or unsaturated alcohol. In this case, the carbon number is 1
If it is 1 or less, the lubricity decreases, and if it has 19 or more carbon atoms, the viscosity of the product becomes too high and the workability decreases. More specifically, preferable examples include lauryl alcohol, palmityl alcohol, myristyl alcohol, oleyl alcohol, and stearyl alcohol.

Examples of the carboxylic acid include the following. It is a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, preferably a fatty acid having 16 to 18 carbon atoms.
At this time, if the range of the number of carbon atoms is lower than the above range, the lubricity is inferior, and if the range is higher, the workability decreases. Specifically, lauric acid, myristic acid, palmitic acid, oleic acid,
Stearic acid and behenic acid can be exemplified.

In the present invention, as the base oil to which the above-mentioned specific compound is to be added, conventionally known base oils may be appropriately used in a wide range, such as mineral oil, beef tallow, palm oil, lard, and fatty acid. It is appropriately selected from esters and the like.

In the present invention, various additives conventionally used in this type of lubricating oil may be appropriately compounded. Examples of the additives at this time include an oiliness improver, a rust inhibitor, an extreme pressure agent, an antioxidant, a surfactant, an antifoaming agent, a preservative, and the like.

[0025]

Next, the present invention will be described in detail with reference to examples. Table 1 shows various physical properties of a specific polycondensate used in the present invention and an ester of the polycondensate (hereinafter, referred to as the compound of the present invention). However, Table 1 also shows the performance of the compound of the oil agent conventionally used for comparison.

[0026]

[Table 1]

However, the methods for measuring the properties in Table 1 are as follows. <Lubricity> Testing machine: two-high rolling mill Roll diameter: 150 mmφ × 200 mm Roll surface; sandpaper # 600 polishing Rolling speed: 13 m / min Test material: ordinary cold-rolled steel plate; thickness 2 mm × width 20 mm × length 250 mm test oil : Undiluted solution 60 ° C Apply test oil to a roll, roll 5 test materials in 3 passes,
It measured from the average rolling reduction and the average load of five test materials, and evaluated from the load of 60% of rolling reduction. Evaluation Criteria: A load at 60% reduction of oleic acid was rated as ○, ◎: lower than oleic acid load, and excellent in rollability ○: load equivalent to oleic acid △: slightly higher load than oleic acid × : Higher load than oleic acid XX: Highest load and poor rollability

<Rust prevention power> Wet box test (JIS-K-2264) Temperature: 49 ± 1 ° C. Humidity: 95% or more Test time: 7 days Test material: Normal cold-rolled steel sheet (thickness 0.8 mm × width 80 mm × (Length: 100mm) Use after polishing the surface with sandpaper # 100. Test oil: 5% of each test agent was dissolved in a mineral oil having a viscosity of 10 mm ² / s (40 ° C.) before use. The test material was immersed in a test oil heated to 60 ° C. for 1 minute, then placed in a wet box, and the state of rust generation after 7 days was evaluated.

<Deterioration resistance> Turbine oil oxidation stability test method (JIS-K-2514) Temperature: 80 ° C. Air blowing amount: 3 l / h Catalyst: Copper, steel wire Test time: 5 days Test oil: viscosity 10 mm ² / S (40 ° C) 5% of each test agent was dissolved in mineral oil and used. The test oil and catalyst were placed in a test tube, and air was blown at a temperature of 80 ° C. Evaluation was made based on the increase in viscosity, the increase in acid value, and the amount of sludge formed after the test for 5 days. Evaluation criteria A: Almost no change was observed. ：: Almost no increase in viscosity and acid value, but sludge formation was observed. Δ: Increase in viscosity and acid value was observed, and a little sludge was generated. X: The rate of increase in viscosity and acid value is high, and a large amount of sludge is generated.

<Melting Point> Rising Melting Point The test agent was left in a freezer at -10 ° C. for one day, placed in a thermostat at a temperature of 20 ° C., and evaluated based on the temperature and fluidity of the test agent.

<Dust of machinery etc.> Dull rolling method Rolling test: 2-high rolling mill Roll diameter: 150 mm φ × 200 mm Roll surface; Dull roll Rolling speed: 13 m / min Test material: Normal pickled steel sheet; thickness 2 mm × width 50 mm × length 500 mm test oil: 5% of each test agent and 3% of an emulsifier were dissolved in mineral oil having a viscosity of 10 mm ² / s (40 ° C.). The test oil was dispersed in water to a concentration of 5%, and the temperature was adjusted to 50%.
While spraying a roll at 10 ° C., dirt on a rolling mill after 10 passes of 10 test materials was evaluated.

The compounds of the present invention shown in Table 1 were each produced by the following methods. <Ricinoleic acid polycondensate> ricinoleic acid in nitrogen stream 2
Heat to 05 ± 10 ° C, acid value about 130,90,45,
30 polycondensates were obtained. <Hydroxystearic acid polycondensate> Hydroxystearic acid was heated to 205 ± 10 ° C. in a nitrogen stream to obtain a polycondensate having an acid value of about 130, 90, 45, or 30. <Ester of hydroxystearic acid polycondensate and oleic acid> Hydroxystearic acid polycondensate (acid value 130)
And oleic acid undergo an ester reaction at about 160 ° C. in the presence of a catalyst (paratoluenesulfonic acid) to give an acid value of 91,
A product with an iodine value of 2.3 was obtained.

Examples 1 to 6 and Comparative Examples 1 to 6 A predetermined amount of each component shown in Table 2 was mixed to prepare a lubricant. Various physical properties were measured for this product. The results are shown in Table 3 and FIG. However, the measuring methods of various physical properties are as follows.

(1) Rolling test Testing machine Two-high rolling mill Roll diameter: 150 mmφ × 200 mm Roll surface: Sandpaper # 600 polishing Rolling speed: 13 m / min Test material Normal cold-rolled steel sheet; thickness 2 mm × width 20 mm × length 250 mm Test oil concentration; 5% Temperature; 50 ° C Five rolled materials were rolled in three passes while spraying test oil.
Rollability was evaluated from the average rolling reduction and the average load of five rolled materials.

(2) Friction coefficient tester Bowden-type adhesion slip tester Sliding speed; 0.33 mm / sec Sliding distance; 30 mm Test material Normal cold-rolled steel sheet; thickness 1 mm × width 20 mm × length 10 mm test ball SUJ-2 3/16 inch Load 3 kg Test oil concentration; 5% Temperature; 50 ° C. Sliding 25 reciprocations, indicated by an average coefficient of friction of 20 to 25 reciprocations.

(3) Scratch prevention testing machine Lubricating oil evaluation testing machine Roll diameter: 76 mmφ × 90 mm Test material Normal cold-rolled steel sheet; thickness 2 mm × width 20 mm × coil Test oil concentration; 5% temperature; 50 ° C. As shown in FIG. Performed by the method. That is, in one stand, the test material is rolled at a speed of 10 m / min without lubrication (the roll of the two stands slides ten times faster than the test material speed). By changing the load of the two stands, the draft of the test material is measured, and the critical draft at which flaws occur is determined. Report at the maximum critical draft at which no flaws occur. However, A in the figure
Is lubricated with a load of 1 ton, and B is supplied with test oil.

(4) Dirt on Machines and Processed Products Testing Machine Dull Rolling Roller Roll Diameter: 150 mm φ × 200 mm Rolling Speed: 13 m / min Test Material Normal Steel Pickling Material; Thickness 2 mm × Width 50 mm × Length 500 mm Test Oil Concentration 5% temperature; 50 ° C. Ten test materials were rolled for 10 passes (rolling rate: about 80%) while spraying test oil, and dirt under the roll (mechanical dirt) and dirt on the test specimen after rolling were visually determined.

(5) Foaming Test The foaming test was performed by the method shown in FIG. However, in FIG. 3, 1 is a heater,
2 is a pump, 3 is a test oil, and 4 is a foam. Test machine Pump circulation method Test oil concentration; 5% Temperature; 50 ° C Test time 20 minutes

[0039]

[Table 2]

Each component in Table 2 is as follows. Synthetic ester A: Oleic acid ester of trimethylolpropane Synthetic ester B: Isostearic acid ester of trimethylolpropane Phosphorus extreme pressure agent: Dioleyl hydrogen diphosphite Anti-rust additive: Triethanolamine salt of dodecyl succinic acid Antioxidation Agent: ter-butylhydroxytoluene Organic amine A: Triethanolamine Organic amine B: Diethanolamine Nonionic surfactant: Polyoxyethylene laurate (HLB = 10.0) Anionic surfactant: Ca-petroleum sulfonate Cationic surfactant: N, N-diethyl 1,3-propanediamide of α-olefin maleic anhydride copolymer Compound A of the present invention: Polycondensate of ricinoleic acid (acid value 47, iodine value 93) Compound B of the present invention: hydroxystearic acid Compound (acid value 48, iodine value 2.6) Compound C of the present invention: hydroxystearic acid polycondensate oleate (acid value 91, iodine value 2.3) Compound D of the present invention: hydroxystearic acid polycondensate (acid value) 35, iodine value 2.0)

[0041]

[Table 3]

The measuring methods and evaluation criteria of various physical properties shown in Table 3 are as follows. Coefficient of friction: Bowden adhesion slide tester, cold rolled ordinary steel sheet, temperature 50 ° C, sliding speed 0.33 mm / sec, concentration 5% Flaw prevention: sliding rolling method, cold rolled ordinary steel sheet (0.4 × 20 × coil mm) Plate: Roll speed ratio = 1: 10, Roll speed 100m / min, Concentration 5%, Temperature 50 ° C Machine and processed product dirt: Dull rolling method, plain steel pickled plate (2 × 50 × 500mm) 10 Rolling speed 13 m / min. Number of passes 10 passes. Concentration 5%. Temperature 50 ° C. Judgment based on dirt on rolling mill and rolled material. ：: Almost no dirt is observed. ○: Dirt is slightly adhered. Dirt adheres thinly on the entire surface XX: A large amount of dirt adheres Foaming property: Circulation method, concentration 5%, temperature 50 ° C Foaming amount ：: Almost no bubbles are observed △: Foam height 20 mm or less ×: Foam height 20 mm taller than

FIG. 1 shows the results of the rolling test. However, 1 to
Numerals 8 are as follows. 1: Comparative example 4: 2: Example 4 3: Comparative example 3: 4: Example 3 5: Comparative example 6: Comparative example 2 7: Example 2 8: Example 1

[Brief description of the drawings]

FIG. 1 shows the results of rolling tests of various lubricants.

FIG. 2 is a schematic view showing a method for measuring flaw prevention.

FIG. 3 is a schematic explanatory view of an example of an apparatus used in a foaming test.

[Explanation of symbols]

 1: Heater 2: Pump 3: Test oil

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mikio Nakamura 1021 Nukatabe-Kitamachi, Yamatokoriyama-shi Daido Chemical Industry Nara Production Engineering Office (72) Inventor Akira Kusumoto 1021 Natabe-Kitamachi, Yamatokoriyama-shi Daido Chemical Nara Production Technology Office

Claims (1)

[Claims] (1) Polycondensate of ricinoleic acid or hydroxystearic acid (B) Said polycondensate and aliphatic carboxylic acid having 12 to 22 carbon atoms or aliphatic alcohol having 12 to 22 carbon atoms A lubricating oil for metal plastic working, comprising at least one of the following esters: