JPH026800B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 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 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 metal rolling oil of the present invention is composed of the following. That is, alkylene oxide is added to a castor oil ester with at least one hydroxyl group remaining in the molecule obtained by reacting castor oil with an unsaturated fatty acid having 12 to 24 carbon atoms, and then the resulting ester is thermally polymerized. obtained, and its viscosity at 40℃ is 300~
It is characterized by using a polymer having a weight of 1800 cst. The present invention uses the above-described polymer as one of the main components, and if necessary, animal and vegetable oils, mineral oils, antioxidants, and surfactants can be mixed therein. Examples of unsaturated fatty acids having 12 to 24 carbon atoms used in the present invention include oleic acid, linoleic acid, linolenic acid,
Representative fatty acids include elaidic acid, ricinoleic acid, and ricinoelaidic acid. When producing esters between these fatty acids and castor oil, these fatty acids may be used as they are in the esterification reaction, but these fatty acids The desired ester can also be obtained by a transesterification reaction as a short-chain alkyl ester of a fatty acid. The esterification reaction can be carried out by a conventional method. That is, the reaction between unsaturated fatty acids having 12 to 24 carbon atoms and castor oil is carried out in the presence of an acidic catalyst such as hydrochloric acid, sulfuric acid, para-toluenesulfonic acid (hereinafter referred to as "PTSA") or an alkaline catalyst such as caustic soda or caustic potash. This is done by heating at ~220°C for 2 to 15 hours. At this time, in order to avoid coloring of the product, it is preferable to carry out the reaction in the presence of an inert gas such as nitrogen gas. In addition, the transesterification reaction between short-chain alkyl esters of fatty acids and castor oil is carried out in the presence of an alkaline catalyst such as caustic soda, caustic potash, or sodium methylate at 40 to 120°C while removing alcohol. It can be carried out. Examples of the alkylene oxide added to the castor oil ester include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides may be used singly, or two or more of them may be added alternately or randomly. The alkylene oxide addition reaction is carried out by a conventional method. That is, an addition reaction product is obtained by reacting an esterified product of castor oil with an alkylene oxide at 110 to 180°C under normal pressure or increased pressure in the presence of an alkaline catalyst such as caustic soda, caustic potash, or sodium methylate. . The number of moles of alkylene oxide added is 2~
The amount is 100 moles, preferably 3 to 60 moles. The polymerization reaction for obtaining the polymer of the present invention is carried out by heating to a high temperature and performing a thermal polymerization reaction. In the thermal polymerization reaction, the double bonds of the unsaturated fatty acids introduced through the esterification reaction and the double bonds of the ricinoleic acid groups in castor oil proceed in a complex manner, but it can be controlled by controlling the reaction conditions. As a result, a polymer having a viscosity suitable for rolling oil can be obtained. In other words, the reaction conditions for thermal polymerization are to heat the obtained ester or polyester as is or in the presence of activated clay at 200 to 300°C for 10 to 30 hours, but the progress of the reaction is usually determined by measuring the viscosity. Check while doing so. The reaction temperature and time are selected depending on the desired viscosity, and the reaction conditions are controlled so that the viscosity of the resulting polymer falls within the range of 300 to 1800 cst (40°C). Control reaction conditions. As the polymer used in the present invention,
An oil having a viscosity within the above range is preferable, and when used as a metal rolling oil, it has good lubricity and pressure resistance, and exhibits excellent rolling performance. The viscosity
When polymerized oil of less than 300cst (40℃) is used as metal rolling oil, both lubricity and pressure resistance are insufficient.
Good rolling performance cannot be obtained. Also, the viscosity
When a polymerized oil exceeding 1800cst (40°C) is used as a metal rolling oil, the friction coefficient and pressure resistance are good, but the degreasing properties of the steel plate after rolling are extremely poor, which has a large negative impact on subsequent processes. The polymer obtained in this way can be used as is in the rolling process to obtain rolling oil with excellent performance. They can also be used in combination. The present invention will be explained below with reference to Examples. The numbers in the examples indicate parts by weight. Example 1 935 parts of castor oil, 568 parts of oleic acid, and 16 parts of PTSA were reacted at 150 to 160°C for 8 hours under a nitrogen gas stream.
An ester with an acid value of 7.8 and a hydroxyl value of 38.0 was obtained.
This ester was reacted with 174 parts of propylene oxide in the presence of caustic potash at 180-200°C. The resulting addition reaction product had a viscosity of 123 cst (40°C), which
Heated and polymerized at 200-220℃ for 20 hours, resulting in a viscosity of 950 cst (40
℃) was obtained. Example 2 935 parts of castor oil, 280 parts of distilled bran fatty acid,
12 parts of PTSA was reacted at 150 to 180°C for 6 hours under a nitrogen gas stream to obtain an ester with an acid value of 2.0 and a hydroxyl value of 92.0. Subsequently, 440 parts of ethylene oxide was added to this ester at 180-200°C in the presence of 2.8 parts of caustic potassium.
The addition reaction was carried out to obtain an acid value of 1.8 and a hydroxyl value of
67.5, an ester with a viscosity of 163 cst was obtained. 40 parts of activated clay was added to this and heated at 210 to 230°C for 15 hours to obtain a polymer having a viscosity of 1050cst (40°C). Example 3 935 parts of castor oil, 423 parts of distilled bran fatty acid,
12 parts of PTSA was reacted at 150 to 180° C. for 6 hours under a nitrogen gas flow to obtain an ester with an acid value of 1.0 and a hydroxyl value of 62.5. Add ethylene oxide 220 to this
(5 moles) followed by 174 parts (3 moles) of propylene oxide in the presence of caustic potash.
The addition reaction was carried out at 200°C to obtain an ester with a viscosity of 108cst (40°C). Add 50 parts of activated clay to this ester and heat at 210-230℃ for 15 hours to obtain a viscosity of 750 cst.
(40°C) was obtained. Example 4 935 parts of castor oil, 423 parts of distilled bran fatty acid,
14 parts of PTSA was reacted at 140 to 150°C for 7 hours under a nitrogen gas stream to obtain an ester with an acid value of 1.5 and a hydroxyl value of 60.8. Next, 2900 parts of propylene oxide was added to this reaction product in the presence of 3 parts of caustic potassium.
The addition reaction was carried out at 180-200°C to obtain an ester with an acid value of 1.0 and a hydroxyl value of 5.6. This ester was heated at 220-230°C for 16 hours to obtain a polymer having a viscosity of 1380 cst (40°C). Example 5 935 parts of castor oil, 282 parts of oleic acid, and 12 parts of PTSA were reacted at 140 to 150°C for 6 hours under a nitrogen gas flow.
An ester with an acid value of 0.5 and a hydroxyl value of 92.0 was obtained.
An addition reaction was carried out with 440 parts of ethylene oxide to this ester in the presence of 2.4 parts of caustic potassium at 180 to 200°C. 40 parts of activated clay was added to this and polymerization was carried out by heating at 200 to 220°C for 20 hours to obtain a polymer having a viscosity of 580cst (40°C). Table 1 shows the polymers obtained in Examples 1 to 5 below.
As shown in Figure 2, the lubrication performance of rolling oil was tested either alone or as a blend.

[Table] The friction coefficient (μ) and pressure resistance of rolling oils No. 1 to 6 were measured, and the results are shown in Table 2. Further, in the rolling test, rolling oils Nos. 1 to 5 were applied in fixed amounts as they were to the rolling material, and No. 6 was supplied as a 15% emulsion. The amount of oil adhering to the rolled material was set to 1 g/m ² for all Nos. 1 to 6. The test results are used to evaluate rolling performance based on the relationship between rolling reduction ratio (%) and rolling load (ton).
It is shown in Figure-1. A commercially available tallow-based rolling oil was used as a comparison sample. The test method regarding the lubrication performance of the rolling oil for steel plates of the present invention is as follows. Friction coefficient test method Soda pendulum type oil tester N-type load-bearing capacity test method Shell type high speed four-ball friction tester Rolling test method Rolling mill: Four-roll rolling machine Work roll diameter 150mm x width 140mm Back-up roll diameter 250mm x width 140
mm Roll material Chrome steel roll circumferential speed 30 m/min Rolling material: SPC-C Thickness 0.6 mm x Width 50 mm x Length 150 mm Measuring method of rolling performance Two 50 mm intervals (l ₁ ) on the steel plate before rolling
A line was drawn, the line was rolled, the distance (l ₂ ) after rolling was measured, and the rolling reduction was determined using the following formula. Rolling ratio (%)=l ₂ −l ₁ /l ₂ ×100 Further, the rolling load (ton) at that time was measured using a load cell.

[Table] Example 7 Using 935 parts of castor oil, 568 parts of oleic acid, and 16 parts of PTSA, an esterification reaction was carried out in the same manner as in Example 1 to obtain an ester, and further propylene oxide was added.
174 parts was subjected to an addition reaction in the same manner as in Example 1, and the viscosity
An unadded reaction product of 118cst (40°C) was obtained. then this
The polymerization reaction was carried out at 200 to 220°C for 3 to 50 hours, and samples were taken as appropriate during the reaction to obtain 212cst (polymer 7-1),
386cst (polymer 7-2), 765cst (polymer 7-3),
1345cst (polymer 7-4), 1720cst (polymer 7-4)
Polymers having viscosities of 5) and 2260cst (polymer 7-6) were obtained. The obtained polymers 7-1 to 7-6 were used alone as a metal rolling oil, and the friction coefficient, pressure resistance, and degreasing property were measured. The results are shown in Table-3.

[Table] Degreasing test method Polymers 7-1 to 7-6 were applied to a test piece (SPC-C, 100 mm x 50 mm x 0.3 mm) at an adhesion amount of 500 mg/m ² )
Apply it so that it looks like this. Next, an alkaline cleaning solution (a 9:1 mixture of 10 mole EO adducts of sodium orthosilicate and nonylphenol) with a liquid temperature of 80°C and a concentration of 5% by weight was sprayed for 30 seconds on the surface of the test piece coated with the above sample. After cleaning the surface of the test piece, the test piece was washed with water and dried. The degreasing rate was calculated from the amount of sample oil applied to the test piece and the weight loss after washing, and the degreasing performance was evaluated according to the following criteria. The degreasing rate was measured five times for the same sample oil, and the average value was used. Evaluation criteria: A: Degreasing rate 98% or more B: 95-98% C: 90-95% D: 90% or less

[Brief explanation of drawings]

The drawing is a rolling performance comparison diagram showing the rolling performance of Examples and Comparative Examples in terms of the relationship between rolling load and rolling reduction.

Claims (1)

[Claims] 1. An alkylene oxide is added to an ester of castor oil with at least one hydroxyl group remaining in the molecule obtained by reacting castor oil with an unsaturated fatty acid having 12 to 24 carbon atoms, and then the resulting product is thermally polymerized. A metal rolling oil characterized by using a polymer having a viscosity of 300 to 1800cst at 40°C.