JPH0336879B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a metal rolling oil composition, and more particularly to an emulsified metal rolling oil composition. [Prior art] Metal rolling oils that have been commonly used have lubricating oil components, usually base oils such as fats, mineral oils, or fatty acid esters, and additives such as rust preventives, extreme pressure agents, oiliness improvers, and antioxidants. Various auxiliary agents are added, and this is supplied to the rolling section as an O/W type emulsion using an emulsifier, usually at a concentration of about 1 to 20%. However, recent advances in rolling technology have led to higher rolling speeds and mass production, and the requirements for rolling oil, such as lubricity, circulation stability, workability, and wastewater treatment properties, have become increasingly severe. At present, there is a need for the development of a rolling oil that can fully meet these demands. However, conventional rolling oils using emulsifiers have various drawbacks and are not satisfactory. In other words, in conventional rolling oil using an emulsifier,
Rolling lubricity was controlled by changing the type and amount of emulsifier added to increase or decrease the amount of oil adhering to the rolling oil and the surface of the rolled material (plate-out amount).
However, in rolling oils using such emulsifiers, the amount of plate-out and liquid circulation stability show contradictory tendencies, and if the stability of the emulsion is improved, plate-out of the rolled material will be reduced. The amount decreases, resulting in insufficient lubricity, and if the amount of plate-out is not increased, the emulsion becomes unstable, causing various problems when recycled. In addition, the generated iron powder adheres to the unstable emulsion, causing so-called rolling stains that stain the cold-rolled steel plate, resulting in the disadvantage that it adversely affects the subsequent cleaning and annealing steps. In addition, it adheres to the rolling mill itself and its surroundings, which not only impairs its aesthetic appearance but also causes operational problems. [Object of the Invention] The present invention has been made through intensive research in order to solve the above-mentioned drawbacks of conventional rolling oils. We have discovered that it is possible to solve this problem and obtain an emulsified rolling oil with excellent liquid circulation stability without reducing the amount of plate-out, and have now completed the present invention. That is, the present invention provides (A) a lubricating oil component that is at least one of animal and vegetable oils, mineral oils, and fatty acid esters, and (B) (a) the following formula: (However, in the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, and one of A is

〔Effect of the invention〕

In the present invention, by using at least one of the specific polymer compounds represented by the above formulas (a) to (c), excellent liquid circulation stability is exhibited without reducing the amount of plateout. . More specifically, in the rolling oil composition of the present invention, the lubricating oil component has a considerably large particle size due to the excellent protective colloid action of the specific polymer compounds represented by formulas (a) to (c) above. It maintains and stably disperses in water, and does not have a broad particle size distribution.
It shows a fairly narrow and sharp distribution and has extremely good circulation stability. In addition, when supplied to the rolling processing section, if the oil particles come into contact with the metal material to be rolled, the large oil particles form a thick and strong lubricating film on the metal material, which has the effect of increasing the amount of plateout. . In addition to the above effects, the rolling oil composition of the present invention exhibits the following excellent effects. (i) The emulsion concentration and the coolant (rolling oil diluted with water during use) are extremely unaffected by temperature, and the state of the emulsion does not change due to temperature changes and can be used stably. This makes rolling work management very easy. (ii) Even if scum or metal powder is mixed in, there is very little change in the particle size of the lubricating oil component in the emulsion, and since the scum and iron powder are made hydrophilic, mill (rolling mill) stains are improved. (iii) Cleanliness of the surface of the metal rolled material is greatly improved. At this time, if the surface of the rolling oil is not cleaned, edge carbon and the like will occur in the subsequent annealing process, which is undesirable. (iv) Lubricity is significantly improved by about 7 to 10% compared to conventional rolling oil. [Structure of the Invention] The rolling oil composition of the present invention basically consists of a lubricating oil component consisting of at least one of fats and oils, mineral oil, and fatty acid ester, and a polymer represented by the above formulas (a) to (c). It contains at least one compound. As the lubricating oil component used in the present invention, any of those conventionally used in this type of rolling oil composition can be used, and typical examples include oils and fats,
Examples include mineral oil and fatty acid ester, and these can be used alone or in a mixed system of two or more. Specifically, mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; animal and vegetable oils such as whale oil, beef tallow, pork oil, rapeseed oil, castor oil, bran oil, palm oil, and coconut oil; beef tallow, coconut oil,
Examples include esters of fatty acids obtained from palm oil, castor oil, etc., and aliphatic monohydric alcohols having 1 to 22 carbon atoms, ethylene glycol, neopentyl alcohol, pentaerythritol, and the like. The method for producing the polymer compound represented by formula (A) used in the present invention is not limited in any way, but it can be produced, for example, by the following method. After dissolving the vinyl ether-maleic acid copolymer in a nonpolar medium such as xylene or n-hexane, it is monoamided with 1.0 to 1.5 equivalents of diamine per repeating unit of the copolymer under heating, usually at about 70 to 200°C. , followed by addition of ethylene oxide, alkylation, amination, conversion to an alkali metal salt, and finally solvent removal. Further, the method for producing the polymer compound represented by formula (b) is not limited, but the following method can be cited as a specific example. The isobutylene-maleic acid copolymer is dissolved in a suitable solvent such as dimethylformamide, and then treated in the same manner as above. In (a) and (c), maleic anhydride is monoamidated with diamine in an organic solvent such as xylene, benzene, hexane, etc., and then vinyl ether monomer or isobutylene and a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile are added. It can also be obtained by solution polymerization or emulsion copolymerization in the presence of. The compound of formula (c) is a compound of formula (a) or formula (b) in which A is
In the case of OH, it has a repeating unit dimerized with a crosslinking agent such as an amino alcohol, a polyhydric alcohol such as a glycol, a polyol, or a diamine. At this time, the dimerization method is performed as follows. The monoamidated product of (a) or (b) is dissolved in an appropriate solvent such as xylene, dimerized with a crosslinking agent such as hexamethylene diamine, amino alcohol, diol, polyol, and polyethyleneimine, and then polyethylene oxide is added. Obtained by alkylation, amination, and alkyl metal salting. It can also be obtained by performing the reaction (a) or (b) after dimerization. The glycols and diamines used include, for example, ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin,
Examples include sorbitol, neopentyl glycol, ethylenediamine, hexamethylenediamine, polyethyleneimine, monoethanolamine, diethanolamine, and the like. Among the compounds of the above formulas (a) to (c) used in the present invention, preferred ones are as follows. That is, first, in formula (a), R ¹ = 3 to 18, m ₁ = 2 to 8, m ₂ = 2 to 10, m ₃ =
2 to 6, R ⁶ = 6 to 18, R ⁷ = 1 to 6, R ⁸ = 1 to 6,
M=Na, n=5 to 1000. Furthermore, the metal represented by M in formula (a) is not limited to the above-mentioned preferred metals, but usually also includes Li and K. In formula (b), n' is preferably 10 to 1,200. In formula (c), preferred is formula (a) or formula
(b) has a dimerized repeating unit, and preferred glycols and diamines used for dimerization are polyethylene glycol, hexamethylene diamine, polyethylene imine, and aminoethyl alcohol. . In the present invention, it is essential to use at least one of the compounds represented by the above general formulas (a) to (c), but preferably these compounds and a substance that forms a counter ion are used in combination. Examples of anions used as counterions include sulfate ion, nitrate ion, chloride ion, glycolate ion, phosphate ion, borate ion, and carbon number 1.
~20 fatty acid ions, etc. Normally, rolling oil is manufactured at the manufacturing plant using fats, mineral oils, esters, etc. as a base oil, and if necessary, one type of oiliness improver, extreme pressure additive, rust preventive additive, antioxidant, emulsifier, etc. A composition containing two or more types is transported by wheel, and it is immersed in water at the site where it is actually used.
It is used after being diluted to a concentration of 0.1 to 10% and emulsionized. Therefore, when a fatty acid ion having 1 to 20 carbon atoms, preferably 8 to 20 carbon atoms, is used as a counterion, the polymeric substances (a) to (c) used in the present invention are uniformly dissolved in the base oil of the rolling oil. . Therefore, at the site of use, like conventional rolling oil, a uniform emulsion can be formed simply by diluting it with water to a predetermined concentration. On the other hand, when counterions other than fatty acid ions having 1 to 20 carbon atoms are used as counterions, polymer compounds (a) to
Since (c) cannot be uniformly dissolved in the base oil, it is preferable to form an emulsion by diluting the rolling oil and the dispersant with water to a predetermined concentration at the site of use. In the present invention, the compounds represented by the above general formulas (A) to (C) may be used alone or in combination of two or more thereof. These polymer compounds of the present invention are blended in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the rolling oil composition. In addition to the above-mentioned components, various known additives such as rust preventive agents, oiliness improvers, extreme pressure agents, antioxidants, etc. can be added to the metal rolling oil composition of the present invention, if necessary. The various additives mentioned above may be added in an amount of 0 to 10%, 0 to 20%, and 0 to 20%, respectively, based on the total amount of the rolling oil composition as necessary.
It can be added at a rate of 3% or 0 to 5%. As rust inhibitors, alkenylsuccinic acid and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate, or other amines, etc.
As oiliness improvers, high fatty acids such as oleic acid and stearic acid and their derivatives, esters or dibasic acids such as dimer acid, are used.As extreme pressure agents, phosphorus compounds such as tricresyl phosphate and Examples of the antioxidant include organic compounds such as zinc dialkyldithiophosphate, phenolic compounds such as 2,4-di-t-butyl-p-cresol, and aromatic amines such as phenyl α-naphthylamine. The metal rolling oil composition of the present invention can be prepared by simply simultaneously mixing the above-mentioned rolling oil components and a water-soluble polymer compound, or by preparing the composition as a concentrated solution with a water content of up to 80%, and adding water to the composition before use. It is used by diluting it with [Example] The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the dispersants A to K used in the following examples are as follows. Polymer dispersant A: Copolymer of oleyl vinyl ether and N,N-diethylaminopropanediamide of maleic anhydride. Degree of polymerization = 8 = 4960 B: N,N-dimethylaminohexamethylene diamide of butyl vinyl ether and maleic anhydride, ethylene Copolymer of 5 mole oxide adduct Polymerization degree = 800 = 355000 C: Copolymer of mono-N,N-dibutylaminodecamethyleneamide of octyl vinyl ether and maleic anhydride Polymerization degree = 160 = 85000 D: Lauryl vinyl ether and anhydride Copolymer of maleic acid N,N-diethylaminopropanamide and oleyl ester Polymerization degree = 40 = 27500 E: Copolymer of isobutylene and maleic anhydride N,N-dimethylaminopropanamide and Na salt Polymerization degree = 400 =111000 F: Copolymer of isobutylene and maleic anhydride, N,N-dimethylaminopropanamide, and dibutylamine Degree of polymerization = 300 (ISCDAM-Am-2) =110000 G: N,N- of isobutylene and maleic anhydride Copolymer of dimethylaminohexamethyleneamide and hexamethyleneamide Polymerization degree = 800 = 305000 H: Copolymer of N,N-dimethylaminopropanamide of oleyl vinyl ether and maleic anhydride (polymerization degree = 8) and hexamethylene diamine Dimerized with =8000 (dimer) I: N,N-dimethylaminopropanamide copolymer of isobutylene and maleic anhydride (degree of polymerization = 30) is converted to polyethyleneimine (=1200)
Dimerized with aminoethyl alcohol = 18000 (dimer) J: Copolymer of N,N-dimethylaminopropanamide of butyl vinyl ether and maleic anhydride (degree of polymerization = 800) was dimerized with aminoethyl alcohol = 525000 (dimer) ) K: Dimerization of N,N-dibutylaminohexamethyleneamide copolymer of oleyl vinyl ether and maleic anhydride (degree of polymerization = 20) with polyethylene glycol (=1000) = 25800 (dimer) Example 1~ 11 Using the above dispersant, a rolling oil composition was prepared by blending the predetermined components shown in Table 1 with the predetermined blending amounts. Various properties were measured for each composition thus obtained. The results are shown in Table 2 and Figures 1-4. However, various characteristics were measured by the following methods. <Amount of adhesion> A pickled plate of 1.6 x 80 x 100 mm was dull rolled for 5 passes, then drained, air dried (24 hours) and weighed to measure _w1 . Then, wash it with Triclean and weigh it.
Measure w ₂ . Coating amount = w ₁ - w ₂ <Rolling test> Using a two-high test rolling mill, 7 rolls were carried out under the following rolling conditions.
Pass rolling was performed, and the rolling load (t number) at elongation rate = 3.4 was measured, and the rolling relative ratio was determined using the following formula. *Rolling conditions Rolling material: Mild steel plate (SPCC) thickness 2.2mm x width 50mm
× Length 500mm Rolling speed: 13m/min Rolling roll: Diameter 150mm, body length 200mm Bright roll Coolant temperature: 50-55℃ Coolant concentration: 5% Emulsion pass schedule: 7 passes *Relative rolling ratio =
Rolling load of the rolling oil of the present invention (number of tons) / Rolling load of commercially available rolling oil (number of tons) <Steel plate brightness test> A commercially available melting tape was applied to the surface of the test-rolled steel plate, then peeled off, and the tape was attached to a standard white mount. The surface pasted on the Nippon Denshoku Kogyo color difference meter ND-
Its brightness was measured using Model 101D. 0 for completely black,
Determine the brightness of the standard white mount as 85. <Deterioration test> The rolling oil of the present invention (3% emulsion) was tested in the following 5th test.
A 7-day deterioration test was conducted using the cyclic deterioration tester shown in the figure, and the particle size distribution before and after the test was measured. However, in Fig. 5, 1 is a tank (liquid temperature 55°C ± 5°C), 2 is a filter, 3 is a pump (25/min), and 4 is a rotating drum (30φcm x 20cm ¹ ). This rotating drum 4 contained 150 1/2 steel balls and 8 cast blocks of 2 cm x 2 cm x 1 cm, and rotated at 115 rpm. The solid lines in Figures 1 to 4 represent the particle size distribution before the test, and the dotted lines represent the particle size distribution after the test.

【table】

【table】

【table】 [Brief explanation of drawings]

1 to 4 are drawings showing the results of deterioration tests for each rolling oil composition, and FIG. 5 is a drawing showing the method of deterioration testing. 1...tank, 2...filter, 3...pump, 4...rotating drum.

Claims (1)

[Scope of Claims] 1 (A) A lubricating oil component that is at least one of animal and vegetable oils, mineral oils, and fatty acid esters, and (B) (a) the following formula: (However, in the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, one of A is [formula], and the other is OH, -O(C ₂ H ₄ O) - _n2 H, -OR ₆ ,OM,
ONH−(CH ₂ )− _n3 NH ₂ , ONH ₂ R ⁶ or
ONHR ⁷ R ⁸ . Further, n is an integer of 10 to 3050, m ₁ is an integer of 2 to 10, m ₂ is an integer of 1 to 20, and m ₃ is an integer of 1 to 10. Furthermore, R ₂ and R ₃ are the same or different H or CH ₃ groups, R ₄ and R ₅ are the same or different alkyl groups having 1 to 3 carbon atoms, and R ⁶ is the same or different alkyl groups having 1 to 3 carbon atoms.
20 alkyl groups, R ⁷ and R ⁸ are the same or different alkyl groups having 1 to 20 carbon atoms, M
(indicates an alkali metal) vinyl ether-maleic acid copolymer having a repeating unit represented by (b) the following formula (However, in the formula, A is the same as above, R ⁹ is H or
CH ₃ and n' is an integer from 10 to 1300); and (c) in the above formula (a) or (b), A is OH, it contains as an essential component at least one kind of isobutylene-maleic acid copolymer or vinyl ether-maleic acid copolymer having repeating units dimerized using an appropriate crosslinking agent. A metal rolling oil composition characterized by: