JP2018012848A - Lanolin fatty acid metal salt and rust-proof oil composition containing the same, and lubricant oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide powdery fatty acid metal salt which is excellent in rust-proofness and lubricity, and easily and transparently dissolves base oil such as mineral oil, synthetic oil and a solvent therein.SOLUTION: Powdery lanolin fatty acid metal salt exhibits excellent rust-proofness and lubricity and easily and transparently dissolves base oil such as mineral oil, synthetic oil and a solvent therein, and a rust-proof oil composition blended with the lanolin fatty acid metal salt or a lubricant oil composition is excellent in stability at the time of storage.SELECTED DRAWING: None

Description

  The present invention relates to a rust preventive oil composition and a lubricating oil composition using a powdered lanolin fatty acid metal salt, which is easily dissolved in a base oil selected from mineral oil, synthetic oil and solvent.

  Conventionally, in the field of metal members such as steel plates, steel wires, bearings, steel balls, guide rails, etc., a rust-preventing oil composition has been used to prevent the occurrence of rust on the members. In addition, when performing plastic working such as press molding, bending molding, pultrusion molding, and ironing, an oil composition that exhibits rust prevention during storage and lubricity during plastic processing must be applied to the plate in advance. Has been made. Such an oil composition is generally blended with a base oil such as mineral oil, synthetic oil or solvent, and a film-forming agent such as oxidized paraffin, wax or petrolatum, and an antirust additive. As one of the rust preventive additives, powdered fatty acid metal salts such as calcium stearate are widely used, but fatty acid metal salts are hardly soluble in mineral oil, synthetic oil, solvent, etc., and are blended oil compositions The appearance and stability during storage were not sufficient.

  Lanolin fatty acid metal salts are already known to exhibit excellent effects as rust-preventing oil compositions and lubricating oil compositions (for example, Patent Documents 1 to 4). Since the oil is diluted with mineral oil, synthetic oil, solvent, etc., there is a problem that undesired components other than lanolin fatty acid metal salt enter during use.

Japanese Patent Publication No.52-14215 JP 2002-302690 A JP 2010-070820 A JP-A-10-273687

  Therefore, the problem to be solved by the present invention is a fatty acid metal salt excellent in rust prevention and lubricity, which is easily and transparently dissolved in a base oil such as mineral oil, synthetic oil or solvent. There is to do.

  As a result of intensive studies, the present inventors have found that the powdered lanolin fatty acid metal salt exhibits excellent rust prevention and lubricity, and dissolves easily and transparently in base oils such as mineral oil, synthetic oil, and solvent. And the rust preventive oil or lubricating oil composition which mix | blended this lanolin fatty-acid metal salt discovered that it was excellent in the stability at the time of storage, and completed this invention.

  The powdered lanolin fatty acid metal salt of the present invention exhibits excellent rust preventive properties and lubricity, and easily and transparently dissolves in base oils such as mineral oil, synthetic oil, solvent, etc. It can be easily blended into the composition, and the resulting oil composition is excellent in stability during storage. Moreover, since components other than the lanolin fatty acid metal salt are not included, there is no mixing of unwanted components.

  The lanolin fatty acid used in the present invention is a fatty acid obtained by hydrolyzing wool fat secreted on the surface of sheep wool. Wool fat may be used as it is, but lanolin obtained by purification such as filtration, decolorization, deodorization, dehydration, solvent extraction, centrifugation, distillation and the like may be used. Lanolin fatty acid can be obtained by hydrolyzing commercially available lanolin, purified lanolin, liquid lanolin, hard lanolin, reduced lanolin, adsorbed lanolin, or the like, but more preferably, purified lanolin or hard lanolin is used. Hard lanolin is a lanolin having a melting point of about 30 to 60 ° C., which is obtained by extracting a relatively high molecular weight component from lanolin by operations such as solvent extraction, centrifugation, and distillation.

  The method for hydrolyzing wool fat or lanolin is not particularly limited, and a known method can be used. For example, it can be obtained by hydrolysis with alkali. As the alkali to be used, sodium hydroxide, potassium hydroxide and the like are common, but other alkalis may be used. Alternatively, it may be hydrolyzed with an acid such as hydrochloric acid, sulfuric acid or phosphoric acid. The hydrolyzed lanolin is separated by solvent extraction or the like, and the soap portion of the fatty acid is neutralized with an acid to obtain a free fatty acid, thereby obtaining the desired lanolin fatty acid. Examples of such lanolin fatty acids include lanolin fatty acids, purified lanolin fatty acids, soft lanolin fatty acids, and hard lanolin fatty acids. The lanolin fatty acids used in the metal salt of the present invention are more preferably lanolin fatty acids from the viewpoint of economy. From the viewpoint of the stability of the rust preventive / lubricating composition, it is a soft lanolin fatty acid, and from the point of extreme pressure of the lubricating composition, it is a hard lanolin fatty acid. Soft lanolin fatty acid is a lanolin fatty acid obtained by extracting a relatively low molecular weight component from lanolin fatty acid by operations such as solvent extraction, centrifugation, and distillation, and has a melting point of about 20 to 50 ° C. Commercial products of these soft lanolin fatty acids include lanolin fatty acid soft (melting point 36 ° C., manufactured by Nippon Seika Co., Ltd.). Hard lanolin fatty acid is a lanolin fatty acid having a relatively high molecular weight component extracted from lanolin fatty acid by operations such as solvent extraction, centrifugation, and distillation, and has a melting point of about 60 to 90 ° C. Examples of commercially available hard lanolin fatty acids include YOFCO lanolin fatty acid HHW and Ecolano FW-HHL (melting point: 76 ° C., manufactured by Nippon Seika Co., Ltd.).

  The method for producing the powdered lanolin fatty acid metal salt of the present invention is not particularly limited, and can be produced by a metathesis method, a melting method, a semi-melting method, a slurry method, a solid phase method, a solvent method and the like according to a conventional method. After saponifying with caustic potash to make an alkali soap, there is a metathesis method in which this is reacted with a metal salt to obtain a metal salt, and a direct method in which a fatty acid is reacted with a metal oxide or hydroxide to obtain a metal salt. The most common.

  Examples of the metal used in the present invention include calcium, zinc, aluminum, barium, magnesium, lithium, iron, lead and the like depending on the intended use.

  The blending amount of the lanolin fatty acid metal salt used in the present invention into the rust-preventing oil composition and the lubricating oil composition can be 0.01 to 50% by weight, preferably 0.1 to 40% by weight, and rust preventive. From the viewpoint of lubricity, it is more preferably 1 to 20% by weight.

  As the base oil constituting the rust-preventing oil composition or lubricating oil composition of the present invention, mineral oils, synthetic oils and solvents that are generally used as base oils for rust preventive oils and metalworking oils can be used. One type of base oil can be used alone, or a plurality of types can be used in combination. Examples of the mineral oil include paraffinic and naphthenic refined mineral oils obtained by purifying a fraction obtained by distilling crude oil. Examples of synthetic oils include hydrocarbon-based, aromatic-based, ester-based, and ether-based synthetic oils and silicone oils. Examples of the solvent include hydrocarbon solvents.

  In the rust preventive oil composition or lubricating oil composition of the present invention, additives that are generally blended in the rust preventive oil composition or lubricating oil composition, as long as the preferred effects of the present invention are not impaired, Japan and other countries Components described in patent publications and patent publications (including publications and republications), for example, film forming agents such as oxidized paraffin, wax, petrolatum, petroleum / synthetic sulfonic acids or salts thereof, aliphatic / Aromatic carboxylic acid or salt thereof, aliphatic / aromatic amine or salt thereof, aliphatic / aromatic ester, aliphatic / aromatic alcohol, aliphatic / aromatic ether, aliphatic / aromatic amide, phosphate ester, Phenol compounds, silicone compounds, triazole compounds, thiazole compounds, sulfur compounds, inorganic salts, inorganic / organic pigments, inorganic / organic dyes, and the like can be blended.

  The rust preventive oil composition of the present invention satisfies all of rust prevention, degreasing, water separation, oil stain resistance, and storage stability, and is suitable as a rust preventive oil for various metal members. Can be used. There are no particular restrictions on the metal member that is the object to be treated. Specifically, it is a cold-rolled steel sheet, hot-rolled steel sheet, high-tensile latter half, galvanized steel sheet, etc. Examples thereof include metal plate materials such as an original plate, an aluminum alloy plate, and a magnesium alloy plate, and further bearing components such as a rolling bearing, a tapered rolling bearing, and a needle bearing, an architectural steel material, and a precision component.

  As rust prevention oil for such metal members, intermediate rust preventive oil used in the process of processing metal members, shipping rust preventive oil used for rust prevention at the time of shipment, before being subjected to press work There are cleaning rust preventive oils used in the cleaning process for removing foreign substances or removing foreign substances prior to shipment in the metal plate manufacturer, but the rust preventive oil composition of the present invention can be used for any of the above applications. .

  The method for applying the rust-preventing oil composition of the present invention to the object to be treated is not particularly limited, and can be applied to a metal member by a method such as spraying, dropping, transferring with a felt material, electrostatic oiling, or the like. . Among these coating methods, the spray method is preferable because the oil film thickness can be made uniform by coating in a fine mist. The application apparatus when applying the spray method is not particularly limited as long as it can atomize the rust preventive oil composition, and for example, any of an air spray type, an airless spray type, a hot melt type and the like can be applied. .

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.

Production Example 1 (Production of Lanolin Fatty Acid Calcium Salt)
Lanolin fatty acid (lanolin fatty acid W saponification value 170, melting point: 60 ° C., manufactured by Nippon Seika Co., Ltd.) 100 g (0.30 mol in terms of saponification value) was dissolved by heating, suspended in 1000 g of hot water, and 25.3 g of 48% sodium hydroxide aqueous solution. (0.30 mol) was added and it stirred at 80 degreeC for 4 hours, and prepared the sodium soap aqueous solution. Separately, 16.8 g (0.15 mol) of calcium chloride was dissolved in 100 g of water to prepare an aqueous calcium chloride solution.
After cooling the sodium soap aqueous solution to a temperature of 70 ° C., the whole amount of the calcium chloride aqueous solution was dropped over 30 minutes, and the mixture was aged by stirring for 1 hour while maintaining the temperature of 70 ° C. The metal salt slurry thus obtained was filtered, and the resulting cake was washed with water until the filtrate had a conductivity of 300 μS / cm or less. Subsequently, the cake was washed in a hot air dryer at 80 ° C. for 48 hours. Dried. The obtained lanolin fatty acid calcium salt was in a powder form and contained 0.1% free fatty acid, 5.8% metal, and 1.4% moisture.

Production Example 2 (Production of Lanolin Fatty Acid Zinc Salt)
A sodium soap solution prepared in the same manner as in Production Example 1 was cooled to 50 ° C, and 20.7 g of zinc chloride dissolved in 100 g of water was added dropwise over 30 minutes to maintain the temperature at 50 ° C. The mixture was aged with stirring for 1 hour. The metal salt slurry thus obtained was filtered, washed with water and dried in the same manner as in Production Example 1 and further pulverized with a miller to obtain a powder. The obtained lanolin fatty acid zinc salt was 2.0% free fatty acid, 8.3% metal, and 0.5% water.

Production Example 3 (Production of hard lanolin fatty acid zinc)
In a pressure reactor, 100 g of hard lanolin fatty acid (lanolin fatty acid HHW acid value 100, melting point 76 ° C., manufactured by Nippon Seika Co., Ltd.) (0.18 mol in terms of acid) was charged and dissolved at 90 ° C. After dissolution, a slurry of 7.3 g (0.09 mol) of zinc oxide and 29 g of water was added, the reactor was sealed, and the temperature was raised to 130 ° C. with stirring and reacted for 1 hour. After that, it was evacuated and dehydrated under reduced pressure to obtain a liquid zinc soap. The liquid zinc soap was pulverized after cooling to powder. The obtained hard lanolin fatty acid zinc salt had a free fatty acid content of 1.8% and a metal content of 5.0%.

Examples 1-3, Comparative Examples 1-3 (Preparation of rust preventive oil composition)
2 g of lanolin fatty acid calcium salt of Production Example 1, 7.5 g of alkylbenzene sulfonate Ca salt (NCP, manufactured by Chemtura Corporation), 3 g of soft lanolin fatty acid pentaerythritol partial ester (manufactured by Nippon Seika Co., Ltd.), and machine oil W10 as a base oil 87.5 g (manufactured by Taniguchi Oil Refinery Co., Ltd.) was added and mixed at normal pressure and 80 ° C. for 0.5 hour to obtain a rust preventive oil composition of Example 1. Similarly, the rust preventive oil compositions of Examples 2-3 and Comparative Examples 1-3 were obtained with the compositions shown in Table 1.

Examples 4-6, Comparative Examples 4-6 (Preparation of lubricating oil composition)
To 0.5 g of lanolin fatty acid calcium salt of Production Example 1 is added 5.0 g of sulfurized lard (GS-110, manufactured by DIC Corporation) and 94.5 g of machine oil W10 (manufactured by Taniguchi Oil Refinery) as a base oil. The lubricating oil composition of Example 4 was obtained by mixing at normal pressure and 80 ° C. for 0.5 hour. Similarly, the lubricating oil compositions of Examples 5-6 and the lubricating oil compositions of Comparative Examples 4-6 were obtained with the compositions shown in Table 2.

Evaluation of Rust Preventive Oil Composition About the rust preventive oil compositions of Examples 1 to 3 and Comparative Examples 1 to 3, the composition appearance, salt spray test (rust preventive test), degreasing test, water by the evaluation methods shown below. A separability test, an oil stain resistance test, and a storage stability test were performed. The results are also shown at the bottom of Table 1.

Evaluation of Lubricating Oil Composition For the lubricating oil compositions of Examples 4 to 6 and Comparative Examples 4 to 6, the composition appearance, quaternary wear test (lubricity), copper plate corrosion test, and storage were evaluated by the evaluation methods shown below. A stability test was performed. The results are also shown at the bottom of Table 2.

(Composition appearance)
The appearance of the obtained oil composition was visually evaluated based on the following evaluation criteria.
A: Uniform and transparent B: Uniform turbidity C: Turbidity precipitation

(Salt spray test)
A commercially available cold rolled steel plate equivalent to SPCC-SD (0.8 mm × 60 mm × 80 mm) was dipped in a rust-preventing oil composition for 1 minute, then pulled up and allowed to stand at room temperature for 24 hours to obtain a coating film of 2 to 3 μm. The test piece thus obtained was subjected to a salt spray test in accordance with JIS K 2246 “Salt spray test method”, and the area ratio of rust after 24 hours and 48 hours was evaluated based on the following evaluation criteria. And evaluated.
A: 0%
B: 1-10%
C: 11-25%
D: 26-50%
E: 51-100%

(Degreasing test)
A commercially available cold rolled steel plate equivalent to SPCC-SD (0.8 mm × 60 mm × 80 mm) was dipped in a rust-preventing oil composition for 1 minute, then pulled up and allowed to stand at room temperature for 24 hours to obtain a coating film of 2 to 3 μm. The test piece thus obtained was immersed for 2 minutes with stirring in a 42 ° C. degreasing solution of FC-L4328 (nonionic alkaline degreasing agent, manufactured by Nihon Parker Rising Co., Ltd.) 2 wt% aqueous solution. After completion of the immersion, the sample was washed in running water for 30 seconds, and the degreasing property was evaluated based on the following criteria by the water wetted area ratio of the test piece after washing with water.
A: 90-100%
B: 60-89%
C: 0 to 59%

(Water separation test)
25 ml of rust preventive oil composition and 25 ml of purified water were collected in a colorimetric tube having a capacity of 50 ml. This sample was kept in a 40 ° C. constant temperature water bath for 30 minutes and then shaken vigorously for 1 minute. After shaking, it was left in a constant temperature water bath at 40 ° C., and the time (minutes) for separating the resulting emulsion into water and oil was evaluated based on the following criteria.
A: Less than 10 minutes B: 10 to 20 minutes C: 21 minutes or more

(Oil stain resistance test)
A commercially available SPCC-SD-equivalent cold-rolled steel sheet (0.8 mm × 60 mm × 80 mm), with 5% purified water added to the rust-preventing oil composition and emulsified, is sandwiched between test pieces, and a 100 g load is applied. The corrosion area after being allowed to stand at 82 ° C. for 24 hours was evaluated based on the following criteria.
A: No corrosion B: Less than 10% corrosion C: 10% or more corrosion

(Storage stability test)
30 g of the oil composition was collected in a glass bottle with a capacity of 50 ml. This sample was kept at 20 ° C. and 50% relative humidity for 12 hours, and then kept at 50 ° C. and 95% relative humidity for 12 hours as one cycle. This cycle was continuously carried out until clouding or precipitation occurred. Repeated. The storage stability of the oil composition was evaluated based on the following criteria from the number of days required until cloudiness or precipitation occurred.
A: 21 days or more B: 15-20 days C: 8-14 days D: 2-7 days E: Within 1 day

(Fourth class wear test)
A shell quaternary test according to ASTM D4172 was performed. The wear area after sliding for 1 hour under the conditions of a load of 392 N, a rotation speed of 1200 rpm, and an oil temperature of 75 ° C. was measured, and the lubricity was evaluated based on the following criteria.
A: Wear area 0.20 mm ² or less B: Wear area 0.21 to 0.30 mm ²
C: Wear area 0.31 mm ² or more

(Copper plate corrosion test)
A copper plate corrosion test was performed. The test temperature was 100 ° C., the test time was 3 hours, and other conditions were evaluated according to JIS K 2513 in the following four stages. The lower the number, the better the corrosion resistance.
A: Slightly discolored B: Moderately discolored C: Darkly discolored D: Corrosion

As can be seen from the results in Tables 1 and 2, the rust-preventing oil composition and the lubricating oil composition of Examples 1 to 6 using powdered lanolin fatty acid metal salts exhibit excellent rust prevention and lubricity. The appearance and storage stability of the composition are higher than those of the rust preventive oil composition and the lubricating oil composition using the fatty acid metal salts (calcium stearate, zinc stearate, calcium oleate) other than the present invention of Comparative Examples 1 to 6. It turned out to be excellent.

Claims (4)

  A powdery lanolin fatty acid metal salt, which is transparently dissolved in a base oil selected from mineral oil, synthetic oil and solvent.   2. The metal salt according to claim 1, wherein the metal is selected from calcium, zinc, aluminum, barium, magnesium, lithium, iron and lead.   A composition in which the metal salt of claim 1 or 2 is transparently dissolved in a base oil selected from mineral oil, synthetic oil and solvent. A rust preventive oil composition or a lubricating oil composition comprising the metal salt of claim 1 or 2, or the composition of claim 3.