JPH0144239B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a rust-preventing lubricant and a rust-preventing lubrication treatment method, and particularly to a rust-preventing lubricant and a rust-preventing lubrication method suitable for use in cold working and the like. [Background of the Invention] As rust inhibitors for steel materials, carboxylic acids and carboxylates (metallic Ca , Ba, Mg, Al, Zn, Pb, etc.), sulfonate (metal such as Na, Ca, Ba,
Additives such as carboxylic acid esters, alkoxyphenylamines, diethanolamine derivatives, amino alcohols, mono- or diphosphoric acid esters, and phosphite esters are known. Rust preventive oil made by blending these additives with mineral oil is applied to the surface of steel materials to suppress the occurrence of rust. However, the rust-preventing performance of rust-preventing oils containing these additives varies considerably depending on the conditions of use. For example, when applied to steel plates, etc., sorbitan partial esters, carboxylic acids, etc.
Z0231) has good rust prevention performance, but it shows poor results in the salt water immersion test method (JIS-Z1801), and there is no rust prevention oil that has excellent rust prevention performance under any usage conditions. In addition, even when a steel plate coated with anti-corrosion oil is processed under low processing conditions such as dye drawing, the lack of lubrication will cause damage to the mold, wear, and breakage of the molded product, making it impossible to process with anti-rust oil alone. Usually, an additional layer of oil is applied. However, there is a problem in that the lubricity of the machining oil is inhibited and seizure is likely to occur.Therefore, there is a need for an excellent rust-preventing lubricant that has rust-preventing and lubricating effects at the same time. On the other hand, a rust-preventing lubrication treatment method for cold working (Japanese Patent Publication No. 19159/1983) has been developed in which the surface of steel products and wire drawings manufactured by hot rolling retains rust-preventing and lubricating functions during the cooling process. Are known. This treatment method involves the cooling process of hot-rolled steel or wire rods from high temperature (600℃) to room temperature.
Immerse in a phosphoric acid aqueous treatment solution containing lubricants such as water-soluble resin, wax, fatty acids, higher fatty acid esters, and metal soap to descale and simultaneously form a film made of phosphorus compounds, resin, and lubricant on the surface of steel and wire. It is something that makes you The steel material after film formation is
Although it has excellent rust prevention performance, if it is used after being cut to the size intended for plastic working, the fractured surface will have no lubricating film, and it will be necessary to perform a new lubrication treatment. In addition, when forming objects with large plastic deformation or complex shapes, the steel material may come into direct contact with the die, causing fatal problems such as seizure. It is desired to develop a rust-preventing lubricant that has the following properties. [Object of the Invention] The object of the present invention is to provide an excellent rust-preventing lubricant that performs rust-preventing and lubricating functions simply by applying it to the surface of a workpiece such as a steel material or steel plate, and a rust-preventing lubrication treatment using the same. How to provide. [Summary of the Invention] The rust-preventing lubricant of the present invention comprises lubricating oil, condensed phosphoric acid, and the general formula (RO) ₃ P... () (R... is an aryl group or an alkyl group) and/or (RO) ₂ PHO is a new rust-preventing lubricating oil that contains one or more phosphite esters represented by () (R...is an aryl group or an alkyl group) and has a synergistic effect of rust prevention and lubrication. . The condensed phosphoric acid used in the present invention includes:
Metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are preferred, but if they do not dissolve in the lubricating oil, they become a dispersion type, so pyrophosphoric acid or polyphosphoric acid is particularly preferred. In addition, as the phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, triisodecyl phosphite, tristearyl phosphite, Trioleyl phosphite, dibutyl hydrogen phosphite, di-2-ethylhexyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite and the like can be mentioned. Lubricating oils used in the present invention include mineral oils, synthetic oils such as polyolefin oils, polyglycol oils, silicate ester oils, diester oils, polyol ester oils, polyphenylene ether oils, fluorine oils, silicone oils, and mixtures thereof. Oil etc. can be used. When insoluble condensed phosphoric acid or phosphite ester is blended into mineral oil, synthetic oil, or a mixed oil thereof, it is preferable to uniformly suspend and disperse it using an emulsifier. The emulsifier can be arbitrarily selected depending on the type of lubricating oil, condensed phosphoric acid, and phosphite ester, but esters of polymeric succinic acid are effective as an example. The rust-preventing lubricant of the present invention has particularly effective rust-preventing and lubricating functions by adding 1% by weight of condensed phosphoric acid to the lubricating oil and adding phosphite in an amount 0.5 times the amount of condensed phosphoric acid added. However, when plastic working of steel materials or steel plates involves a high degree of processing or when molding parts with complex shapes, the amount of condensed phosphoric acid added to the lubricating oil is 3 to 6% by weight, and the amount of condensed phosphoric acid added to the phosphite ester is of
It is preferable to add 1.5 to 4 times the amount from the viewpoint of effectiveness and economy. The rust-preventing lubricant of the present invention may be applied to the surface of steel materials, steel plates, etc. by brushing, spraying, or dipping in the rust-preventing lubricant. In addition, the rust-preventing lubricant of the present invention or the steel material to be plastically worked,
Plastic working can be performed after heating one of the steel plates and immersing the metal material in lubricating oil to form a reaction film with rust prevention and lubricant coating on the metal surface. In this case, the temperature of the rust-preventing lubricant, steel material, steel plate, etc. is preferably 50 to 150°C. [Embodiments of the Invention] Examples 1 to 12 The composition of the present invention shown in Table 1, consisting of 88% by weight of mineral oil having a viscosity of 150 mm ² /S at 40°C, 4% by weight of pyrophosphoric acid, and 8% by weight of phosphite ester. After applying the steel plate for rust prevention test and the material for machining performance test by dip coating during rust prevention lubrication, the rust prevention performance was determined by wet test method and containment test method.
In addition, the processing performance by the forward extrusion processing method was evaluated. The evaluation results are shown in Table 1. The evaluation of rust prevention performance and processing performance was conducted under the following conditions. <Test method for rust prevention performance> (1) Wet test method (based on JIS-Z-0228) This test evaluates the rust prevention performance under high temperature and high humidity conditions. Test piece size 20mm x 40
mm 2m thick chromium molybdenum steel (SCM415)
A set of 5 pieces were immersed in oil for 1 minute, and after draining the oil, they were hung in a constant temperature and humidity chamber at a temperature of 50°C and a humidity of 95% or higher for 20 days, and the state of rust formation on the test piece surface was examined. Ta. (2) Storage test method (based on JIS-Z0231) This test evaluates the rust prevention performance under storage conditions where it is not exposed to direct light or wind and rain. The test pieces were of the same size and material as in the wet test method, coated with oil, and hung in a room for 60 minutes.
The state of rust formation on the surface of the test piece after being left for days was investigated. (3) Machining performance evaluation method (3-1) Machining conditions

【table】

[Table] (3-2) Processing performance A band heater 2 for heating the mold is attached to the mold 1 shown in the figure, and the mold temperature is increased step by step by 5 to 10°C, and the material 3 coated with lubricating oil is placed in a container. 4, and lactone hydraulic press (processing speed, approximately 5 mm/
20 pieces were processed at a time using a 100-second machine (seconds), and the highest mold temperature at which no burning phenomenon occurred on the surface of the processed material was measured. The higher the temperature, the better the processing performance of the lubricating oil. (4) The lubricating oils used in the comparative examples are all rust-proof press working oils, but the blending ratio is unknown. Comparative example 1 Base oil: Mineral oil Additive: Chlorine compound, sulfur compound Rust inhibitor: Contained Comparative example 2 Base oil: Mineral oil Additive: Chlorinated hydrocarbon, fatty acid, oleic acid, ester Rust inhibitor: Contained From Table 1 As is clear, the rust-preventing lubricating oil of the present invention is superior to the comparative example in terms of rust-preventing performance and machining performance for steel materials.

[Table] ◎...No rust, ○...1-2 spots of slight rust △...1 or more spots of rust with a diameter of 1-4 mm, ×...Examples of rust occurring over 1/4 of the test piece area 13-27 Base oil The viscosity at 40℃ is 100mm ² /S
polyolefin oil, 58mm ² /S polyol ester oil, 200mm ² /S polyphenyl ether oil,
The rust-preventing lubricating oil of the present invention shown in Table 2, consisting of 88% by weight of silicone oil of 200 mm ² /S and polyglycol oil of 85 mm ² /S, 4% by weight of pyrophosphoric acid, and 8% by weight of phosphite ester, was carried out. The rust prevention performance and processing performance on steel materials were evaluated in the same manner as in Examples 1 to 12. The evaluation results are shown in Table 2. From the results in Table 2, the rust-preventing lubricating oil of the present invention is superior to the comparative example shown in Table 1 in terms of rust-preventing performance and machining performance on steel materials, regardless of which base oil is used. I understand that.

[Table] Examples 28 to 43 Rust-preventing lubricating oils of the present invention were obtained by adding pyrophosphoric acid and dioleyl hydrogen phosphite to mineral oil having a viscosity of 150 mm ² /S at 40° C. in amounts shown in Table 3. This was subjected to a wet test under the same conditions as Example 1.
Rust prevention properties and processing performance were evaluated by storage tests. The results are shown in Table 3. As is clear from Table 3, the rust prevention properties and processing performance for steel materials show very good results when the amount of pyrophosphoric acid is 3% by weight and the amount of dioleyl hydrogen phosphite added is at least 1.5 times that of pyrophosphoric acid. Further, even when the amount of pyrophosphoric acid added is 2% by weight and the amount of dioleyl hydrogen phosphite added is the same as that of pyrophosphoric acid, the rust prevention properties and processing performance are superior to those of the comparative examples shown in Table 1.

【table】

[Table] Examples 44 to 65 Mineral oil with a viscosity of 150 mm ² /S at 40°C, 100 mm ² /S
The rust-preventing lubricating oil of the present invention, in which metaphosphoric acid, polyphosphoric acid, and triisodecyl phosphite are added to S polyolefin oil, 58 mm ² /S polyol ester oil, and 200 mm ² /S silicone oil in the amounts shown in Table 4. I got it. This was evaluated for wetness test and processing performance under the same conditions as in Example 1. The results are shown in Table 4. As is clear from the results in Table 4, the rust resistance
It can be seen that the machining performance is excellent.

【table】

[Table] Example 66 A test piece for rust prevention evaluation and a test material for machining performance evaluation were placed in a rust prevention lubricant having the same composition as Example 12.
Immerse the items heated to 50℃ and 150℃ for 1 minute,
Rust prevention properties and processing performance were evaluated under the same conditions as in Example 1. As a result, no rust was observed in the wet test method even after being left for 20 days. Further, as a result of evaluating the workability under the same processing conditions as in Example 1, the workability showed a good result of 350°C. [Effects of the Invention] As explained above, according to the present invention, both rust prevention and lubrication functions can be achieved simply by applying a rust preventive lubricant to the steel surface, so there is no need for conventional rust preventive treatment or phosphate coating. This has the effect of eliminating the need for lubrication and significantly reducing production costs.

[Brief explanation of drawings]

The figure is a cross-sectional view of a forward extrusion mold for evaluating the machining performance of rust-preventing lubricants. 1...Mold, 2...Mold heating band heater, 3...
Material, 4... Container, 5... Processing tool section.

Claims (1)

[Scope of Claims] 1. A rust-preventing lubricating oil characterized in that the lubricating oil contains condensed phosphoric acid and a phosphite ester of the following formula () and/or (). (RO) ₃ P ... () (RO) ₂ PHO ... () (In each formula, R is an aryl group or an alkyl group) 2 Condensed phosphoric acid and the following formula () and/or ()
A rust-preventing lubrication treatment method comprising heating either a phosphite-containing lubricating oil or a steel material to form a rust-preventing lubricant film on the surface of the steel material. (RO) ₃ P ... () (RO) ₂ PHO ... () (R in each formula is an aryl group or an alkyl group)