JPH0214957B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a lubricant used when processing metals, and more particularly to a lubricant used when processing stainless steel and non-ferrous metals, such as aluminum, copper, and their alloys, particularly during cold rolling. It is something. Generally, metal processing methods include rolling, drawing, pressing, cutting, drawing, and eyeloning, and lubricants suitable for each method are used. In particular, hot rolling and cold rolling are performed in the rolling process of metal, that is, rolling metal with a rolling machine to make a thin metal plate, and various lubricants are used in cold rolling. There is. Lubricants are also used in hot rolling for aluminum and its alloys. In cold rolling of metal, the metal plate is often annealed to reduce its hardness in order to prevent hardening of the processed surface after rolling. The properties required of a lubricant used in such metal processing, especially in cold rolling of metals, are good rolling properties, that is, high oiliness and oil film strength, good cooling properties, and The finished surface (glossy) must be good, the lubricant must be stable, safe and have a long service life, it must adhere well and evenly to the metal surface, the lubrication must be easy and economical, and the lubricant must be stable, safe and have a long service life. These include not producing hard-to-remove dirt called oil stain, and not causing rust on metal materials and rolling mill parts.
In recent years, cold rolling mills have become faster and the deformation heat and frictional heat generated during plastic working have increased, so cooling performance and heat safety have become particularly important among the properties required of lubricants. . Conventionally, low-viscosity mineral oils have been used as lubricants for cold rolling because the lower the viscosity, the greater the cooling properties.However, low-viscosity mineral oils also have a low flash point, which poses a risk of fire during high-speed rolling. There is sex. Therefore, taking advantage of water's excellent fire safety and cooling properties, mineral oil-based or oil-based soluble oils are used, which are made by dispersing or emulsifying low-viscosity mineral oil, palm oil, beef tallow, or other fats and oils in water. I started it. For example, mineral oil-based soluble oil is made by mixing low-viscosity mineral oil with an emulsifier and adding it to water, stirring and mixing. However, mineral oil-based soluble oils have poor lubricity, and various additives, particularly metal additives, may cause oil stains during the annealing process, which is considered a major drawback. On the other hand, oil-based soluble oils are also widely used and are attracting attention for their excellent lubricity, but they have the disadvantage that a uniform emulsion cannot be obtained unless the oil is supplied while being constantly heated and stirred during use. Further, cleaning methods for preventing oil stains include alkaline, solvent, and electrolytic cleaning, but these methods require considerable equipment and labor, but have not yet achieved a sufficient cleaning effect. The present inventors have conducted extensive research to solve the above-mentioned problems with conventionally known lubricants for metal processing, particularly lubricants for metal cold rolling, and have completed the present invention. The present invention has extremely good cooling properties and fire prevention properties during high-speed rolling in metal processing, especially cold rolling of metals, and has excellent rolling properties, rust prevention properties, and emulsion stability, and also has excellent oil stain resistance due to annealing treatment. Provides a lubricant for metal processing of metals, especially stainless steel and non-ferrous metals such as aluminum, copper and their alloys, which has various characteristics such as less generation and extremely good surface condition of the metal after rolling. The purpose is to That is, the present invention includes two inventions, and the specific invention is: (a) 100 parts by weight of an aliphatic monohydric alcohol having 8 to 22 carbon atoms; (b) 0 to 0 mineral oil having a viscosity of 1.5 to 35 cst at 40°C.
800 parts by weight, (c) 0.1 to 100 parts by weight of aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms, its anhydride or its ester, (d) General formula R ₁ [-O-(R ₂ O) _n −R ₃ ] _o (In the above formula, R ₁ and R ₃ are hydrogen, a hydrocarbon group, or an acyl group, R ₁ and R ₃ may be the same or different, and R ₂ is an alkylene group. is the basis,
A lubricant stock solution containing 0.1 to 200 parts by weight of a surfactant (n is 1 to 6, m x n is 1 to 20) is emulsified in 4 to 1000 times the weight of water. The second invention provides a lubricant for metal processing, which comprises: (a) 100 parts by weight of an aliphatic monohydric alcohol having 8 to 22 carbon atoms; (b) a lubricant having a viscosity of 1.5 to 35 cst at 40°C. Mineral oil 0~
800 parts by weight, (c) 0.1 to 100 parts by weight of aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms, its anhydride or its ester, (d) General formula R ₁ [-O-(R ₂ O) _n −R ₃ ] _o (In the above formula, R ₁ and R ₃ are hydrogen, a hydrocarbon group, or an acyl group, R ₁ and R ₃ may be the same or different, and R ₂ is an alkylene group. is the basis,
n is 1 to 6, m x n is 1 to 20) 0.1 to 200 parts by weight of a surfactant, (e) 1 to 250 parts of polybutene with a number average molecular weight of 250 to 3000.
The present invention provides a lubricant for metal working, which is obtained by emulsifying a lubricant stock solution containing 4 to 1000 parts by weight of water. Hereinafter, the metal working lubricant according to the present invention will be explained in more detail. Component (a) as used in the present invention refers to aliphatic monohydric alcohols having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and mixtures thereof. As the aliphatic alcohol, any of saturated alcohols, unsaturated alcohols, and mixtures thereof can be used, but saturated alcohols are preferred from the viewpoint of thermal stability. Further, as the aliphatic alcohol, any of straight chain alcohols, branched alcohols, and mixtures thereof can be used. Can be used in the present invention
Examples of the alcohol component (a) include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol,
Tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), eicosyl alcohol, docosyl alcohol, octadecenyl alcohol (oleyl alcohol), octadecyl alcohol Examples include decatrienyl alcohol (linoleyl alcohol) and mixtures thereof. As the alcohol of component (a) in the present invention, alcohols manufactured by any method, whether natural or synthetic, can be used. For example, sodium reduction and/or hydrogenation of natural oils such as coconut oil and beef tallow can be used. Mixed alcohols obtained by the method, oxo alcohols synthesized by the oxo method, and synthetic alcohols derived from ethylene and metal alkyl by the Ziegler method can be used. In the present invention, the aliphatic monohydric alcohol used as component (a) must have 8 to 22 carbon atoms, and those with more than 22 carbon atoms are solid even at room temperature and have poor workability. Moreover, oil stains are likely to occur during annealing.
Further, those having less than 8 carbon atoms have poor rolling properties and have a irritating odor, resulting in poor workability. Furthermore, if this component (a) is not used, the rolling properties of the lubricant will decrease, and the water emulsifying properties of the lubricant stock solution will also deteriorate, which is not preferable. Component (b) in the present invention is 1.5 to 1.5 at 40°C.
Mineral oil having a viscosity range of 35 cst, preferably 2.0 to 15 cst. As the mineral oil for component (b), any type of mineral oil can be used as long as it is within the above viscosity range, but the lubricating oil fraction obtained by distilling crude oil may be subjected to any refining process, such as solvent refining. It is preferable to use mineral oil obtained through , sulfuric acid treatment, hydrogenation refining, clay treatment, etc. The amount of component (b) is 0 per 100 parts by weight of component (a).
~800 parts by weight, preferably 30-300 parts by weight, more preferably 50-150 parts by weight. Component (b) does not necessarily need to be used, but within the above range.
By adding it to component (a), the viscosity of the lubricant can be adjusted, and the adhesion between the rolling mill roll and the metal plate can be further improved in the rolling process. However, if the blending amount of component (b) exceeds the above range, rolling properties will deteriorate, oil stains are likely to occur due to annealing treatment, and emulsifying properties of the lubricant stock solution will also deteriorate, which is not preferable. Component (c) in the present invention refers to an aliphatic dicarboxylic acid having an alkyl group or an alkenyl group having 8 to 22 carbon atoms, preferably 9 to 20 carbon atoms, an anhydride thereof, an ester thereof, or a mixture thereof. be. Succinic acid is particularly preferably used as the aliphatic dicarboxylic acid. When succinic acid is used as the aliphatic dicarboxylic acid, the anhydride of the aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms as component (c) in the present invention is represented by the following general formula. It is a chemical compound. (In the formula, R represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably 9 to 20 carbon atoms.) Also, an aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms or an ester thereof It refers to a compound represented by the following general formula. (In the formula, R represents the same alkyl group or alkenyl group as above. R′ and R″ may be the same or different, and hydrogen, an alkyl group having 1 to 10 carbon atoms, or

[Formula] is shown. However, R represents hydrogen or a methyl group, and n represents an integer of 1 to 5. ) In the above formula, any R (alkyl group or alkenyl group having 8 to 22 carbon atoms) can be used, but those made from oligomers of propylene or butene or those made from linear olefins are suitable. preferable. Further, as the ester, either diester or monoester (half ester) can be used, but it is more preferable to use monoester from the viewpoint of rust prevention. Particularly preferred compounds as component (c) in the present invention are alkyl succinic acids, alkenyl succinic acids, these acids and ethylene glycol,
These are propylene glycol, polyethylene glycol, esters with polypropylene glycol, and mixtures thereof. The blending amount of component (c) is 0.1 per 100 parts by weight of component (a).
~100 parts by weight, preferably 1 to 50 parts by weight, more preferably 4 to 20 parts by weight. If component (c) is not used, or if the amount of component (c) is less than the above range, the rust prevention properties of the lubricant will be weak, causing rust to form on the equipment around the rolling mill, and resulting in poor rolling properties. This is not preferable because it lowers the temperature. On the other hand, even if the blending amount of component (c) exceeds the above range, the antirust properties and rolling properties of the lubricant will not change much, so there is no need to use such a large amount of component (c). The component (d) in the present invention is a surfactant represented by the general formula R ₁ [-O-(R ₂ O) _n -R ₃ ] _o (1). In formula (1), R ₂ is an alkylene group, and the alkylene group preferably has 2 to 8 carbon atoms, and alkylene groups having different carbon numbers may exist in one molecule. Particularly preferred alkylene groups are ethylene and propylene groups, and preferred polyoxyalkylene groups are polyoxyethylene groups,
They are a polyoxypropylene group and a polyoxyethylene-polyoxypropylene group. In formula (1), R ₁ and R ₃ are hydrogen, a hydrocarbon group, or an acyl group, and R ₁ and R ₃ may be the same or different. The hydrocarbon group referred to here means (i) a saturated or unsaturated linear or branched chain hydrocarbon group having 4 to 22 carbon atoms, preferably derived from an aliphatic monohydric alcohol having 10 to 18 carbon atoms; (ii) di- to hexahydric alcohols, preferably glycol, glycerin, trimethylolpropane, pentadecyl, hydrocarbon residues derived from erythritol and sorbitol; and (iii) substituted or unsubstituted aromatic hydrocarbon groups having 6 to 22 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as phenyl groups. , octylphenyl group, nonylphenyl group, decylphenyl group and dodecylphenyl group. The acyl group referred to herein is preferably one derived from a carboxylic acid having 2 to 22 carbon atoms, particularly a saturated monocarboxylic acid or an unsaturated monocarboxylic acid having 2 to 18 carbon atoms, such as acetic acid. , propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. The R ₁ and R ₃ may be the same or different,
They are arbitrarily selected from hydrogen, a hydrocarbon group, and an acyl group, but it is preferable that one is hydrogen and the other is a hydrocarbon group or an acyl group. In addition, in formula (1), n is 1 to 6, preferably 1
It is an integer from 1 to 3, and m×n each represents an integer from 1 to 20, preferably from 2 to 14. As component (d) in the present invention, a surfactant represented by formula (1) or a mixture thereof can be used, but a particularly preferred surfactant represented by formula (1) is polyoxyethylene. , polyoxypropylene or polyoxyethylene-polyoxypropylene lauryl ether, myristyl ether, palmityl ether, stearyl ether, octyl phenyl ether, nonylphenyl ether, lauryl ester, myristyl ester, palmityl ester, stearyl ester, or these m is an integer of 2 to 14 and n is 1 in formula (1). The blending amount of component (d) is 0.1 per 100 parts by weight of component (a).
~200 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 30 parts by weight. If component (d) is not used, or if the amount of component (d) is less than the above range, the emulsion stability will deteriorate, making it difficult to manage the lubricant, which is not preferable. On the other hand, if the blending amount of component (d) exceeds the above range, plate-out properties during rolling will deteriorate, resulting in poor rolling properties, which is not preferable. In addition to component (d) of the present invention, examples of surfactants include higher fatty acid alkali metal salts (Setsuken),
Anionic surfactants such as alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, higher amine halogenates, alkylpyrinidium halides, quaternary ammonium salts, quaternary phosphonium salts, tertiary A large number of surfactants are known, including cationic surfactants such as grade sulfonium salts, polysoaps, and polyamines, nonionic surfactants such as polyoxyalkylene phosphates, and amphoteric surfactants such as higher alkylamino acids and polyacrylamides. However, if a surfactant other than component (d) of the present invention is used in place of component (d), the emulsion stability of the lubricant will be poor, making it difficult to manage the lubricant. Undesirable. However, in the present invention, a small amount of a surfactant other than the component (d) as shown above may be used in combination with the component (d). In addition, component (e), which is an essential component of the second invention of the present invention, has a number average molecular weight of 250 to 3000, preferably 1000 to 3000.
2500 polybutene. This polybutene is a colorless or slightly yellow transparent liquid polymer obtained by polymerizing an isobutylene-n-butylene mixture mainly composed of isobutylene, and in the present invention, commercially available polybutene can be used. Furthermore, as component (e), it is also possible to use hydrogenated polybdenum, which is made into a saturated hydrocarbon by hydrogenating the terminal double bond of polybdenum using a known method such as a nickel or nickel molybdate catalyst. Even if only a predetermined amount of the components (a) to (d), which are essential components of the specific invention of the present invention, are blended, the lubricant stock solution can be emulsified in water to produce a metalworking lubricant that satisfies various performance requirements. However, by further blending a predetermined amount of component (e) polybutene, a metalworking lubricant with improved rolling properties can be obtained. If the number average molecular weight of component (e) is less than 250, the lubricant will not have the ability to improve properties such as rollability or lubricity, and if the number average molecular weight exceeds 3000, it will adhere to the rolling roll. This is not preferable because it becomes sticky and oil stains are likely to occur during annealing. The blending amount of component (e) is 1 to 250 parts by weight, preferably 10 to 100 parts by weight, and more preferably 15 to 50 parts by weight per 100 parts by weight of component (a). If the blending amount of component (e) is less than the above range, there will be no blending effect of component (e), while if the blending amount of component (e) exceeds the above range, the rolling roll may become sticky or the annealing process may be difficult. This is undesirable because oil stains tend to occur and the emulsifying properties of the lubricant stock solution deteriorate. The lubricant stock solution as used in the present invention is obtained by mixing predetermined amounts of the above-mentioned components (a) to (d) or (a) to (e). Known lubricant additives such as pressure agents, antioxidants and fungicides or preservatives may also be included. Examples of oily agents that can be used in the present invention include higher fatty acids having 8 to 18 carbon atoms, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, and combinations of these fatty acids with carbon atoms of 1 to 18. 8 with aliphatic alcohols or glycols, such as methyl laurate, butyl laurate, butyl stearate, pentyl oleate, octyl myristylate, sorbitan monolaurate, sorbitan monopalmitate, oleic acid monoglyceride, oleic acid diclyceride In addition, animal oils such as beef tallow, lard, mutton fat, fish fat, and whale oil; vegetable oils such as olive oil, coconut oil, castor oil, rapeseed oil, palm oil, and soybean oil; and mixtures thereof. On the other hand, as an extreme pressure agent, for example, n-
Butyl di-n-octyl phosphinate, di-n
- Organic phosphorus compounds such as butylhexylphosphonate, di-n-butylphenylphosphonate, tricresyl phosphate, dibutylphosphoramidate, amine dibutyl phosphate, organic halogen compounds such as chlorinated paraffin, chlorinated diphenyl, sulfide , disulfide, diester disulfide, and other organic sulfur compounds. In addition, examples of antioxidants include N,
Aromatic amines such as N'-di-sec-butyl-p-phenylenediamine and phenyl-α-naphthylamine, and hindered phenols such as 2,6-di-tert-butyl-p-cresol are used as fungicides. Examples of preservatives include phenolic compounds such as O-phenylphenol and tetrachlorophenol, and formaldehyde donor compounds such as 2-hydroxymethyl-2-nitro-1,3-propanediol. These known lubricating oil additives may be used alone or in combination. The amount of this lubricant additive and mixture thereof can be determined arbitrarily, but it is usually based on 100 parts by weight of the lubricant stock solution.
The amount is 15 parts by weight or less, preferably 10 parts by weight or less. The lubricant for metal processing of the present invention is prepared by emulsifying this lubricant stock solution (which may also include the above-mentioned known lubricating oil additives) in water in an amount of 4 to 1000 times by weight, preferably 10 to 100 times by weight. It is obtained by Any method can be used to emulsify the lubricant stock solution in water, and any known method can be used, but representative methods include mechanical emulsification and transfer emulsification. These methods may be used alone or in combination. Further, mechanical emulsification methods include, for example, a homomixer, a bulb homogenizer, a colloid method, and an ultrasonic method. However, the present invention is not limited in any way to the emulsification method, and any method that can produce a uniform emulsion may be used. Furthermore, the metal processing lubricant of the present invention is not only suitable for cold rolling processing of metals, but also for hot rolling processing, drawing processing, etc.
It is also preferably used as a lubricant in other metal processing such as pressing, cutting, drawing, eyeloning, etc., and its use is not limited to metal cold rolling. Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the following examples do not limit the present invention in any way. Examples Metalworking lubricants according to the present invention (invention products 1 to 6) were prepared according to the compositions shown in Table 1. For comparison, products without the addition of component (c) (Comparative Products 1 and 2) and products similar to commercially available products (Comparative Products 3 to 5) were also prepared according to the compositions shown in Table 2. Inventive products 1 to 6, comparative products 1 to 6, and comparative product 1
~5 is the lubricant stock solution shown in Tables 1 and 2.
It is emulsified in twice its weight of water. Next, the results of various tests conducted on products 1 to 6 of the present invention and comparative products 1 to 5 are shown below. 1 Emulsion stability test Inventive products 1 to 1 in a graduated cylinder with a capacity of 100ml
10 ml of the lubricant stock solutions of Comparative Products 1 to 6 and Comparative Products 1 to 5 were added thereto, and then 90 ml of water was added thereto, followed by thorough shaking for 20 seconds. Then leave this at room temperature for 24 hours,
Thereafter, the state of separation of the oil layer and water layer of the lubricant (emulsion stability) was observed and compared. Separation state of oil layer and water layer Inventive product 1 Not separated 〃 2 〃 〃 3 〃 〃 4 〃 〃 5 〃 〃 6 Comparative product 1 Not separated 〃 2 Not separated 〃 3 minutes Separated 〃 4 Slightly separated 〃 5 Slight separation 2 Rolling test A rolling test was conducted using a rolling mill using products 1 to 6 of the present invention and comparative products 1 to 5, and the rolling reduction ratio (difference between the thickness of the metal material before rolling and the thickness of the metal material after rolling) was The rollability was compared by measuring the ratio (expressed as a percentage divided by the sheet thickness before rolling).
It shows that the higher the rolling reduction ratio of a lubricant with respect to rolling load/plate width, the better the metal plate is rolled.
It was determined that the rollability was excellent. Specifications of the rolling mill used Two-high rolling mill Work roll diameter 204 mm Width 220 mm Rolling speed 100 m/min Rolled metal material Aluminum plate A1200, H material Plate width 100 mm, plate thickness 0.4 mm, Length 300 m Lubricating material Lubricant is applied to aluminum by spraying. Figure 1 shows inventive products 1 to 6 and comparative products 1 to 5.
The relationship between rolling load/plate width and rolling reduction ratio is shown. 3 Plate Gloss Test The plate gloss of the aluminum plate rolled by the rolling test in 2 was visually observed and compared. Board Gloss Invention product 1 Good 〃 2 〃 〃 3 〃 〃 4 〃 〃 5 〃 〃 6 〃 Comparative product 1 Fair 〃 2 〃 〃 3 Poor 〃 4 〃 〃 5 Good As is clear from the above results In addition, the metal processing lubricant according to the present invention (product of the present invention) has excellent rolling properties compared to comparative products, and also has excellent properties such as emulsion stability and sheet gloss after rolling. There is. In addition, compared to Inventive Products 1 to 3, Inventive Products 4 to 6 have even better rolling properties, clearly demonstrating the effect of blending polybutene as component (e).

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【table】 [Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between rolling load/plate width and rolling reduction in rolling tests of products 1 to 6 of the present invention and comparative products 1 to 5.

Claims (1)

[Claims] 1 (a) Aliphatic monohydric alcohol having 8 to 22 carbon atoms
100 parts by weight, (b) Mineral oil with a viscosity of 1.5 to 35 cst at 40°C.
800 parts by weight, (c) 0.1 to 100 parts by weight of aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms, its anhydride or its ester, (d) General formula R ₁ [-O-(R ₂ O) _n −R ₃ ] _o (In the above formula, R ₁ and R ₃ are hydrogen, a hydrocarbon group, or an acyl group, R ₁ and R ₃ may be the same or different, and R ₂ is an alkylene group. is the basis,
A lubricant stock solution containing 0.1 to 200 parts by weight of a surfactant (n is 1 to 6, m x n is 1 to 20) is emulsified in 4 to 1000 times the weight of water. A lubricant for metal processing. 2 (a) Aliphatic monohydric alcohol having 8 to 22 carbon atoms
100 parts by weight, (b) Mineral oil with a viscosity of 1.5 to 35 cst at 40°C.
800 parts by weight, (c) 0.1 to 100 parts by weight of aliphatic dicarboxylic acid having an alkyl group or alkenyl group having 8 to 22 carbon atoms, its anhydride or its ester, (d) General formula R ₁ [-O-(R ₂ O) _n −R ₃ ] _o (In the above formula, R ₁ and R ₃ are hydrogen, a hydrocarbon group, or an acyl group, R ₁ and R ₃ may be the same or different, and R ₂ is an alkylene group. is the basis,
(n is 1 to 6, m×n is 1 to 20) 0.1 to 200 parts by weight of a surfactant, (e) 1 to 250 parts of polybutene with a number average molecular weight of 250 to 3000;
A lubricant for metal working, characterized in that it is made by emulsifying a lubricant stock solution containing 4 to 1000 parts by weight of water.