JPS6358874B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to metal rolling oil. Conventionally, palm oil has been used as a rolling oil for steel plates for a long time, but instead, animal and vegetable oils such as beef tallow, lard, Nagasu whale hardened oil, mineral oils, or mixtures of these oils are used as base oils, and additives and oil-based oils are used as rolling oils. Products containing improvers, antioxidants, surfactants, etc. are widely used. On the other hand, the progress of rolling machinery equipment has progressed significantly, and as mills have become larger, there has been a demand for rationalization and precision of the rolling process, such as reducing the number of passes, increasing rolling speed, and increasing the standard accuracy of rolled products. As a result, the conditions for rolling oil are becoming more severe.
Palm oil and tallow-based rolling oils are no longer able to satisfy this condition, but at present no alternative rolling oil has yet been found. The present invention aims to provide a rolling oil that has better rolling performance than conventional palm oil or beef tallow-based rolling oils and can satisfy the harsh rolling processes currently required. The rolling oil of the present invention is composed of the following. At least 1 in 1 molecule obtained by reacting an aliphatic carboxylic acid having 12 to 22 carbon atoms with a polyamine.
A compound obtained by reacting a compound obtained by adding an alkylene oxide to an amide compound in which active hydrogens remain (hereinafter abbreviated as AO adduct) and a diisocyanate compound having two isocyanate groups. It is a metal rolling oil characterized by the use of the following: If necessary, extreme pressure additives, surfactants, antioxidants, etc. can be added to the metal rolling oil. The aliphatic carboxylic acids having 12 to 23 carbon atoms used in the present invention include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. and unsaturated fatty acids such as arachidonic acid. Next, an aliphatic carboxylic acid having 12 to 22 carbon atoms is reacted with a polyamine to obtain an amide compound in which at least one amine group remains in the molecule.The polyamine used here is ethylenediamine,
propylene diamine, hexamethylene diamine,
Examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. The above amide compound has a polyamine and a carbon number
It is obtained by performing an amide reaction with 12 to 22 aliphatic carboxylic acids. To give an example of the reaction conditions, the number of moles of aliphatic carboxylic acid is determined and used in the reaction so that at least one amine group remains in the molecule per mole of polyamine. For example, add 1 mole of lavric acid to 1 mole of ethylenediamine, and add it under a nitrogen gas stream.
The desired amide compound is obtained by reacting at a temperature of 140 to 260°C for 2 to 25 hours. The number of amine groups remaining in the amide compound molecule is calculated from the amine value. Next, an alkylene oxide is added to this amide compound to obtain an AO adduct. The addition reaction of alkylene oxide to this amide compound is also carried out by a conventional method. Examples of the alkylene oxide used here include ethylene oxide and propylene oxide, and these alkylene oxides may be added alone or in a random or block manner, and the number of moles added is The amount is from 2 to 100 mol, preferably from 3 to 60 mol. The AO adduct obtained as described above is reacted with a diisocyanate compound having two isocyanate groups to obtain a compound used in the metal rolling oil of the present invention. The reaction between the AO adduct and the diisocyanate compound is obtained by adding 0.3 to 2 moles of the diisocyanate compound to 1 mole of the AO adduct and reacting at 60 to 100°C. Examples of the diisocyanate compound having two isocyanate groups in the present invention include methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, methoxyphenylene diisocyanate, and biphenyl diisocyanate. If amines remain in the resulting reaction product, generally known treatments such as neutralization, quaternization, and amphotericization may be performed as necessary using processing agents suitable for each treatment. After doing so, it can be used. By performing these treatments, the hydrophilicity of the reaction product can be adjusted appropriately according to the usage conditions, and the polarity of the reaction product can also be adjusted to control adsorption to metal surfaces. You can also do it. These reaction products have high performance as rolling oil when used as is, but they can also be used by mixing with conventional rolling oil, and if necessary, extreme pressure additives, surfactants, and antioxidants may be added. It is also possible to use a mixture of the following. The present invention will be explained in more detail with reference to Examples below. Synthesis Example 1 After reacting 400 parts of lauric acid and 103 parts of diethylenetriamine at 140 to 160°C under a nitrogen gas stream for 2 hours, and further reacting at 180 to 200°C for 4 hours, 440 parts of ethylene oxide was added at 160 to 180°C. , acid value 2.6,
A compound with a hydroxyl value of 72 was obtained. Next, 112.5 parts of 4,4' diphenylmethane diisocyanate was added to 100 to 110 parts of
It was added dropwise at a temperature of 0.degree. C., and after the completion of the addition, the reaction was carried out at 110 to 120.degree. C. for 2 hours to obtain a compound having an acid value of 0.9 and a hydroxyl value of 6.0. Synthesis example 2 568 parts of stearic acid, 103 parts of diethylenetriamine
After reacting for 8 hours at 220-240°C under a nitrogen gas stream, 220 parts of ethylene oxide was added at 160-180°C, and then 174 parts of propion oxide was added at 170-240°C.
An addition reaction was carried out at 190°C to obtain a compound with an acid value of 1.2 and a hydroxyl value of 79.5. Next, 105 parts of naphthalene diisocyanate was added dropwise at 110 to 120°C, and after the addition was completed, the mixture was reacted at 120 to 130°C for 4 hours to obtain a compound having an acid value of 2.4 and a hydroxyl value of 10.5. Synthesis Example 3 After reacting 684 parts of behenic acid and 146 parts of triethylenetetramine at 200 to 240°C under a nitrogen gas stream for 20 hours, 880 parts of ethylene oxide was added at 160 to 180°C to obtain a compound with an acid value of 3.5 and a hydroxyl value of 63. The compound was obtained. Next, 98 parts of methylene diisocyanate was added to 100 to 110 parts of
The mixture was added dropwise at 110°C to 120°C for 3 hours to obtain a compound having an acid value of 2.6 and a hydroxyl value of 4.3. Example 4 282 parts of oleic acid, 116 parts of hexamethylene diamine
After reacting for 10 hours at 180 to 190°C under a nitrogen gas stream, 870 parts of propylene oxide was added at 170 to 180°C to obtain a compound with an acid value of 1.5 and a hydroxyl value of 85.8.
Next, 110 to 174 parts of tolylene diisocyanate
It was added dropwise at 120°C, and after the completion of the dropwise addition, the reaction was carried out at 120-130°C for 4 hours to obtain a compound having an acid value of 1.0 and a hydroxyl value of 3.8. Synthesis Example 5 After reacting 894 parts of ricinoleic acid and 232 parts of pentaethylenehexamine at 190 to 200°C in a nitrogen gas stream for 8 hours, 880 parts of ethylene oxide was further reacted with 160 to 232 parts of pentaethylenehexamine.
Addition reaction at 180℃, then propion oxide
580 parts were added at 180-190°C to obtain a compound with an acid value of 1.5 and a hydroxyl value of 130. Next, 168 parts of hexamethylene diisocyanate was added dropwise at 100 to 110°C.
After dropping, react at 110 to 120℃ for 2 hours to determine the acid value.
1.2, and a compound with a hydroxyl value of 80.2 was obtained. Synthesis Example 6 After reacting 200 parts of lauric acid and 60 parts of ethylenediamine at 150 to 160°C under a nitrogen gas stream for 8 hours, 440 parts of ethylene oxide was added at 140 to 150°C,
A compound with an acid value of 1.8 and a hydroxyl value of 160.0 was obtained. Then 190 parts of methoxyphenyl diisocyanate was added to 110 to 190 parts of methoxyphenyl diisocyanate.
It was added dropwise at 120°C, and after the completion of the addition, the reaction was carried out at 120-130°C for 3 hours to obtain a compound with an acid value of 1.3 and a hydroxyl value of 5.7. Friction coefficient (μ) of Examples 1 to 6 of rolling oil having the composition shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 6,
Pressure resistance was measured, and the results are shown in Table 2 along with the measurement results for tallow-based rolling oil as a comparative example.
In addition, rolling performance tests were conducted by applying a certain amount of rolling oil to the rolled material as it was for Examples 1 and 2, and by supplying it as a 5% concentration emulsion for Examples 3 to 5 and Comparative Examples. . The amount of oil attached to the rolled material was set to 1 g/m ² in all Examples 1 to 6 and Comparative Example. Test results are shown in rolling reduction ratio (%) and rolling load (ton)
The relationship between the rolling performance and the rolling performance is evaluated and shown in Figure 1. The test method regarding the lubrication performance of the rolling oil of the present invention is as follows. Friction coefficient (μ) test method Soda pendulum type oil tester N type load-bearing capacity test method Shell type high speed four-ball friction tester

【table】

[Table] Rolling test method Rolling machine: Four-high roll rolling machine Work roll diameter 150mm x width 140mm Back-up roll diameter 250mm x width 140mm Roll material Chrome steel Roll circumferential speed 30m/min Rolling material: SPC-C Thickness 0.6mm × 50 mm × Length 150 mm Method for measuring rolling performance Draw two lines with a spacing of 50 mm (l ₁ ) on the steel plate before rolling, roll this, measure the spacing after rolling (l ₂ ), and use the following formula. The rolling reduction ratio was determined. Rolling ratio (%)=l ₂ −l ₁ /l ₂ ×100 Further, the rolling load (ton) at that time was measured using a load cell.

[Brief explanation of the drawing]

FIG. 1 is a rolling performance comparison diagram showing the rolling performance of Examples 1 to 6 of the rolling oil of the present invention and a comparative example based on the relationship between rolling load and rolling reduction.

Claims (1)

[Claims] 1. A compound obtained by further adding an alkylene oxide to an amide compound in which at least one active hydrogen remains in one molecule, which is obtained by reacting an aliphatic carboxylic acid having 12 to 22 carbon atoms with a polyamine; having two isocyanate groups,
A metal rolling oil characterized by using a compound obtained by reacting with a diisocyanate compound.