JPS6326160B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel metal plastic working oil composition. Therefore, it is an object of the present invention that the lubricating oil component is in a stable dispersion state in water, has good adhesion when being supplied to the working part during plastic working, and has good adhesion to the metal produced during plastic working. It is an object of the present invention to provide a metal plastic working oil composition which has the property of preventing the contamination of so-called "dirt" components such as powder, deteriorated lubricating oil components, and bearing oil, and which can be reused. The metal plastic working oil composition of the present invention is particularly useful for rolling,
Used as a lubricant for plastic working of metals under high pressure such as drawing, drawing, and wire drawing. Conventionally, water-based lubricants used when plastic working metals include, for example, rolling oil used when cold-rolling steel plates. The former uses triglyceride, and the latter uses petroleum hydrocarbon as a lubricating oil component, to which oiliness improvers, extreme pressure agents, antioxidants, etc. are added. It is usually used as a 1-20% oil-in-water emulsion. However, such conventional emulsion type lubricants
It had various problems and was not satisfactory. A lubricant for metal plastic working intervenes to lubricate the contact area between the tool and the workpiece, and plays the role of preventing direct contact between the tools and the workpiece under high load conditions. In recent years, in order to improve productivity, there has been an increase in demands for increased processing speed, high workability, and surface finish.
Requirements for lubricants are also becoming stricter. Until now, in order to reduce the occurrence of seizure between the tool and the workpiece that occurs during such high-load, high-speed machining, a strong solid lubricant film has been developed between the two objects under high temperature and high pressure. Solid lubricants that form and prevent contact between two objects have been studied. For example, when coating a workpiece by coating or spraying, a solid lubricant is added to mineral oil, fat, ester, wax, etc., and in the case of a water-based lubricant, this is emulsified and dispersed with an emulsifier. Therefore, when a solid lubricant is added to oil and used in an aqueous system, the selection of the type and form of the solid lubricant is also an important factor. Since the effect will only be seen when the product is used, the nature of the water system in which it is actually used is very important. In other words, in the case of lubrication in which lubricating oil is emulsified or dispersed in water, the lubricating oil is supplied in a dispersed state in water, so even if the lubricating oil components have the same composition, the stability of the dispersed particles may vary. Due to gender differences,
Since the amounts of oil adhering to the surfaces of the tool and the workpiece differ, the amount of lubricating oil taken into the contact area between the tool and the workpiece differs, and as a result, the lubricating properties also differ. Even when solid lubricant is added to oil and used in a dispersed manner, if a large amount of oil is taken into the contact area between the tool and the workpiece, the amount of solid lubricant taken in at the same time will increase. This increases the probability that it will contribute to the friction surface between the two bodies, the tool and the workpiece, when the workpiece undergoes plastic deformation, and as a result, the lubrication conditions will also be improved. Therefore, when using a lubricating oil containing a solid lubricant dispersed in water, it is desirable to make the system as unstable as possible to increase the amount of adhesion. It is desirable that the material be stable and easy to handle when it is used in circulation and when it is used in circulation. In addition, lubricating oil is generally used in circulation for a long period of time, and during continued use, so-called "dirt" such as scum and dirty oil, as well as fine metal powder, bearing oil, and antirust oil, become mixed in. When such "dirt" gets mixed into the lubricating oil and adheres to tools and workpieces, it adversely affects the lubricating properties and impairs the cleanliness of the surface. Therefore, it is desirable that the lubricant has the property of being able to separate and float to the upper layer or settle to the lower layer and be easily removed, without these dirt components being mixed into the lubricant during cyclic use. Generally speaking, a lubricating oil containing a solid lubricant is made by adding an emulsifier and emulsifying it in water to form an emulsion.
Emulsion stability (E・S・I) is often adjusted by adjusting the HLB balance (usually HLB 8 to 14). However, with emulsified lubricants in which lubricating oil components are emulsified in water using an emulsifier, the amount of adhesion and the increase in E・S・I tend to contradict each other. If the amount of emulsion adhered to the tools and workpieces decreases, the lubricity becomes insufficient, and if the amount of adhesion does not increase, the emulsion becomes unstable, causing various problems when recycled. Furthermore, when a solid lubricant is added to oil, only the oil is emulsified by the emulsifying action of the emulsifier, and the solid lubricant becomes hydrophilic and tends to be dispersed alone in water, so it will not work with tools along with the attached oil. It is often incorporated between the workpiece and the effect of contributing to improving the lubricating properties cannot be fully demonstrated. In addition, emulsion-type lubricants generate scum or floating oil due to polymerization and decomposition of the emulsion during circulation, resulting in a decrease in emulsion concentration and poor lubricity, resulting in accidents such as seizure and the loss of expensive tools. In addition to causing damage, seizure marks appear on the workpiece, which deteriorates the properties of the product. Furthermore, the lubricant itself is contaminated by the above-mentioned scum, floating oil, fine metal powder, bearing oil, anti-corrosion oil, etc., and the dirt is trapped in the emulsion by the action of the emulsifier. Since it is difficult to separate, the contaminant components increase with repeated use and re-adhesion to tools and workpieces is unavoidable. Under these circumstances, the present inventors conducted intensive research to improve the above-mentioned drawbacks found in conventional emulsion-type lubricants. The lubricating oil component containing the solid lubricant is dispersed in water in the form of a protective colloid. Unlike conventional products, only the oil is emulsified and the solid lubricant is not dispersed alone in the water. Also, unlike conventional emulsions, the oil particles are dispersed in water with a relatively large particle size, so they have good adhesion to tools and workpieces that require high energy during machining. This action prevents the coalescence of oil particles, making it stable, and it also has the excellent properties of being less likely to be contaminated with dirt components than when using emulsification, and even if they are mixed in, they can be easily separated. I discovered that. Therefore, the present invention provides one or more liquid components selected from the group consisting of mineral oils, oils and fats, and fatty acid esters, with an average particle size of 0.01 insoluble therein.
1 or 2 selected from ~200μ solid lubricants
A lubricating oil component containing at least one solid component, as well as the following group having a molecular weight of 250 to 25,000 in an amount of 0.5 to 20% by weight based on the lubricating oil component: (a) Olefin-maleic acid copolymer salt ( b) acrylic acid or methacrylic acid-maleic acid copolymer salt; (c) acrylic acid or methacrylic acid homopolymer salt or copolymer salt thereof; (d) aromatic compound sulfonic acid-formalin condensate salt. The present invention provides a metal plastic working oil composition containing one or more anionic polymer dispersants as an essential component. Examples of the liquid component which is a lubricating oil component of the metal plastic working oil composition of the present invention include mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; whale oil, coconut oil, rapeseed oil, castor oil, rice bran oil; Animal and vegetable oils such as palm oil and beef tallow; cow fingers, coconut oil,
Fatty acids and _C1 obtained from palm oil, castor oil, etc.
_-C22 aliphatic monohydric alcohols, esters with ethylene glycol, neopentyl glycol, pentaerythritol. Examples of solid components include graphite, sulfur, molybdenum disulfide, tungsten disulfide, borates, carbon fluoride, mica, and metal oxides such as MgO, CaO, and Fe ₂ O ₃ . The average particle size of these solid components is preferably 0.01 to 200 μm. Each of the liquid component and the solid component may be used singly, or two or more thereof may be used in combination.
Further, the amount of the solid component contained in the liquid component is preferably 0.1 to 20% by weight based on the lubricating oil component. Even if the solid component is used in an amount of 20% by weight or more, particularly excellent effects cannot be obtained and it is economically meaningless. Specifically, the anionic polymer dispersant used in the present invention is as follows. (a) Olefin-maleic acid copolymer salt For example, an alkali metal, ammonium or amine salt of a copolymer of maleic acid and an olefin having 2 to 20 carbon atoms, with an average molecular weight of 250 to 25,000. (b) Acrylic acid or methacrylic acid-maleic acid copolymer salt, for example, an alkali metal, ammonium or amine salt of the copolymer with an average molecular weight of 500 to
25000 things. (c) A homopolymer salt of acrylic acid or methacrylic acid or a copolymer salt thereof For example, an alkali metal, ammonium or amine salt of the polymer or copolymer salt having an average molecular weight of 500 to 25,000. (d) Aromatic compound sulfonic acid-formalin condensate salt For example, one or two of naphthalene sulfonic acid, creosote sulfonic acid, cresol sulfonic acid, alkylnaphthalene sulfonic acid having an alkyl group having 1 to 4 carbon atoms, or lignin sulfonic acid. Condensate of the above and formalin (degree of condensation 2~
50) alkali metal, ammonium or amine salts. Among the above anionic polymer dispersants, (a) to (c)
Particularly preferred are those having a molecular weight of 2,000 to 10,000. These anionic polymer dispersants are one or two types.
A mixture of two or more types can be used, and this is used in an amount of 0.5 to 20% by weight based on the lubricating oil components. In addition, in the present invention, together with the anionic polymer dispersant, a molecular weight of 3000 to 20000 and an HLB of 18
The above polyoxyethylene type surfactants can be used in combination. These surfactants include the following. For example, polyoxyethylene alkyl ether; polyoxyethylene alkyl allyl ether such as polyoxyethylene alkyl phenyl ether, polyoxystyrenated phenol, polyoxyethylene benzylated phenol; polyoxyethylene alkyl amine, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether; Oxyethylene alkyl sulfate, polyoxyethylene alkyl phosphate, polyoxyethylene alkyl ether carboxymethylated salt, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, oxyethylene oxypropylene copolymer. Here, examples of the salt include alkali metal, ammonium or amine salts, and examples of the alkyl group include those having 2 to 20 carbon atoms, and the number of moles added to ethylene oxide is selected so that HLB is 18 or more. It will be done. Among the above polyoxyethylene type surfactants, especially polyoxyethylene sorbitan fatty acid ester; polyoxyethylene alkyl allyl ether such as polyoxystyrenated phenol and polyoxyethylene benzylated phenol; polyoxyethylene fatty acid ester, polyoxyethylene Sorbitol fatty acid ester and polyoxyethylene alkylamine are preferred. In addition to the above-mentioned components, the metal plastic working oil composition of the present invention may contain various known additives as necessary, such as rust preventives, oiliness improvers; phosphorus compounds such as organic phosphate esters, zinc dialkylthiophosphate, etc. extreme pressure agents such as; antioxidants such as aromatic amines, etc. may also be added. The metal plastic working oil composition of the present invention can be prepared by simply mixing the above-mentioned lubricating oil component and an anionic polymer dispersant, or by preparing it as a concentrated solution with a water content of up to about 80%, and then preparing the composition by simply mixing the above-mentioned lubricating oil components and an anionic polymer dispersant. Use by diluting with. The metal plastic working oil composition of the present invention has a low surface tension (20 to
35dyne/cm). Natural emulsification or emulsification and dispersion by simple stirring cannot be expected, but due to the strong protective colloidal dispersion power of the anionic polymer dispersant, the lubricating oil components that have been made into fine particles by specified mechanical stirring are stabilized as they are, and the particles Even if they agglomerate, they do not easily coalesce and form an oil layer, but are uniformly dispersed in water by constant stirring. The lubricating oil component particles produced in this way have a larger particle size than conventional emulsified particles, so they adhere well to tools and workpieces that have high energy during machining, and have excellent lubrication properties. shows. In addition, due to the action of the anionic polymer dispersant, the "dirt" components do not aggregate with the lubricating oil dispersion particles, and there is no entrainment phenomenon like in emulsified emulsions, so the lubricating oil components are not contaminated. It never happens. Further, the lubricating oil component dispersed particles have a large particle size and easily float to the upper layer to form a creaming layer when left still, so they can be easily separated from the water layer and have excellent wastewater treatment properties. As mentioned above, the metal plastic working oil composition of the present invention has excellent features not found in conventional emulsion type metal plastic working oils. Examples will be further described below. The metal plastic working oil compositions shown in Table 1 were used in the examples.

【table】

[Table] (Note) In this table, solid components, hydrophilic dispersants, and emulsifiers are as follows. 〓 Solid component (1): Graphite (particle size 0.5~
100μ) 〓 Solid component (2): Sodium borate (particle size 0.1
~20μ) 〓 Solid component (3): Molybdenum disulfide (particle size 0.5
~50μ) 〓 Solid component (4): Tungsten disulfide (particle size
0.5～100μ) 〓〓Hydrophilic dispersant (A): Average molecular weight (・) 3500
Sodium salt of a copolymer of maleic acid and isobutylene. 〓〓Hydrophilic dispersant (B): - Triethanolamine salt of a copolymer of 6000 acrylic acid and methacrylic acid equivalents. 〓〓Hydrophilic dispersant (D): 3900, water-soluble surfactant of polyoxyethylene alkylamine with HLB19.5. 〓〓Hydrophilic dispersant (C): ・Sodium salt of 1500 acrylic acid and maleic acid copolymer. Emulsifier: Nonionic surfactant of polyoxyethylene nonyl phenyl ether with HLB 10.8 (M/W485). Example 1 Dispersion stability and oil adhesion test: The metal plastic working oil compositions shown in Table 1 were tested for dispersion stability and oil adhesion using the methods shown below. The results are shown in Table 2. (a) Dispersion Stability Test The metal plastic working oil composition and water were mixed to a predetermined concentration and stirred with a homomixer at a rotation speed of 5000 rpm for 5 minutes, and then stirred at a rotation speed of 500 rpm for 1 hour. 1
After a period of time, the particles were visually observed and evaluated according to the following criteria, and the average particle diameter was measured using a Coulter counter. Evaluation methods were classified into the following three levels. ○: Uniformly dispersed layer with almost no separated floating substances observed in the upper layer. Δ: Uniformly dispersed layer with a small amount of separated floating matter observed in the upper layer. ×: The water portion is separated and an oil layer or solid aggregate is formed. (b) Oil adhesion test method A metal plastic working oil composition and water are mixed to a predetermined concentration and stirred with a homomixer at a rotation speed of 5000 rpm to prepare a dispersion. The adhesion test was carried out by spraying the above dispersion on the test piece using a gear pump for 2 seconds (pressure 1.0 atm, spray rate 1/min), drying at room temperature, and measuring the amount of adhered oil by gravimetric method. I did it. The test pieces used were SPCC,
S, D (JIS G 3141), plate thickness 1mm, size width 50
mm x length 100 mm and surface roughness of 4.0 to 5.0 μm, which was previously degreased with a solvent before use.

[Table] Example 2 Lubrication performance test: A lubrication performance test was conducted on the metal plastic working oil compositions shown in Table 1. The results are shown in Table 3. (1) Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard NDS.
XXK2740 Oil film strength test method (Soda four-ball test method)
It was carried out in accordance with. The test samples were prepared by diluting each metal plastic working oil composition with water to a concentration of 3 wt%, and stirring this with a homomixer at a rotation speed of 5000 rpm. To apply the test sample, spray the above stirred solution at a rate of 0.1/ml (pressure: 2.5 kg/ml).
cm ² ), using a gear pump at a dispersion temperature of 30°C, pass the three test steel balls fixed with a ball holder from below through the space at the center of the three contact points to the rotating steel ball above. It depends on the method of application. (2) Anti-seizing load test (Falex test method) The anti-seizure load was measured in accordance with ASTM standard D-3233 pressure load test (Falex test). The test samples were prepared by diluting each metal plastic working oil composition with water to a concentration of 3 wt%, and stirring this with a homomixer at a rotation speed of 5000 rpm. The test sample was applied using a gear pump at a spray rate of 0.1/ml (pressure: 2.5 kg/cm ² ) and a dispersion temperature of 30°C, and applied to the rotating pin at the center of the fixed block. Yotsuta.

[Table] As is clear from Table 3, when the composition of the present invention is used as a lubricating oil, it is superior to the emulsion type metal plastic working oil using a conventional emulsifier as shown in Comparative Product (1). It showed excellent lubrication performance. Even when comparing product 1 of the present invention and comparative product (1), which have the same lubricating oil components, the former using a water-soluble dispersant has better oil plate-out properties than the latter using an emulsifier. It can be seen that this improves the lubrication performance.
Also, when comparing the products of the present invention and comparison products (2) and (4), the former with added solid lubricant showed much better lubrication performance than the latter without additive. Example 3 Wastewater treatment test: To a sample solution (1000 ml) prepared in the same manner as the oil adhesion test, ±3 g of ban sulfate was added, stirred for 2 minutes, and then calcium hydroxide was added to adjust the pH to 7.
After stirring for 10 minutes, the mixture was left to stand for 30 minutes. After standing still, the subnatant liquid was collected and COD (potassium permanganate method) was measured. The results are shown in Table 4.

[Table] As is clear from the wastewater treatment test results in Table 4, the composition of the present invention generally has better wastewater treatment properties than a dispersion using an emulsifier represented by comparative product E.

Claims (1)

[Scope of Claims] 1. One or more liquid components selected from the group consisting of mineral oil, oil and fat, and fatty acid ester,
A lubricating oil component containing one or more solid components selected from solid lubricants with an average particle size of 0.01 to 200μ insoluble in these, and a molecular weight of 0.5 to 20% by weight based on the lubricating oil component. is 250 to 25,000, (a) olefin-maleic acid copolymer salts, (b) acrylic acid or methacrylic acid-maleic acid copolymer salts, (c) homopolymer salts of acrylic acid or methacrylic acid, or A metal plastic working oil composition containing as an essential component one or more anionic polymer dispersants selected from these copolymer salts (d) aromatic compound sulfonic acid-formalin condensate salts.