JPS6325638B2 - - 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 extreme pressure additives are added to them. , oiliness improvers, antioxidants, surfactants, etc. are widely used. On the other hand, the progress of rolling machinery equipment has been remarkable, and with the increase in the size of mill stands, rationalization and precision of the rolling process are required, 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 oils have become more severe, and palm oil and beef tallow-based rolling oils are no longer able to satisfy these conditions, but there are still rolling oils that can replace them. The current situation is that it has not been released. In addition, the inventors of the present application have previously reported castor oil or a fatty acid ester of castor oil to which alkylene oxide has been added as having excellent lubricity (Japanese Patent Publication No. 52-20430). The rolling oil used in this invention was not sufficiently suitable for high speed rolling under high pressure and high speed, and there was a need for further improvement. The base oil for rolling oil that meets the above characteristics is required to have high oil film strength and maintain it without breaking even during high-speed lubrication. It is conceivable that the material has properties such as high adhesive strength, high viscosity, and a certain degree of molecular weight, and as a result of studies focusing on the above points, the present invention was arrived at. By polymerizing castor oil or fatty acid ester of castor oil to which alkylene oxide has been added to a viscosity of 300 to 1800cst (40℃) and increasing the molecular weight, adhesion and oil film strength are increased, and the friction coefficient and pressure resistance are increased accordingly. The present invention was completed based on the discovery that the lubrication properties such as rolling strength and rolling load can be further improved. The purpose of the present invention is to have a lubricating performance superior to conventional palm oil or tallow-based rolling oils, or substituted fatty acid esters of castor oil, and to be suitable for the harsh rolling process currently required. The objective is to provide a satisfactory rolling oil. The present invention consists of (A) castor oil, (B) castor oil to which alkylene oxide has been added, (C), (A) or (B) and carbon number 4.
(A) of a partial ester in which at least one hydroxyl group remains in the molecule obtained by reacting with -60 monocarboxylic acid or polyhydric carboxylic acid,
(B) and (C) A polymer obtained by thermally polymerizing a reaction product obtained by performing an esterification reaction with an unsaturated fatty acid having 12 to 24 carbon atoms and at least one selected from the three groups is used. The present invention relates to a metal rolling oil for high pressure rolling with excellent lubrication performance. 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. The alkylene oxide-added castor oil of the present invention can be obtained by adding alkylene oxide to castor oil by a conventional method. In addition, partial esters obtained by reacting castor oil or castor oil derivatives with monocarboxylic acids or polyhydric carboxylic acids having 4 to 60 carbon atoms can be produced by an esterification reaction by conventional dehydration condensation. It can also be obtained by transesterification using lower alkyl esters of fatty acids. In addition, the reaction product obtained by reacting at least one selected from (A), (B), and (C) with an unsaturated fatty acid having 12 to 24 carbon atoms or an ester thereof can be subjected to an esterification reaction by a conventional method. You can get it by doing it. Examples of monocarboxylic acids or polycarboxylic acids having 4 to 60 carbon atoms used here include capric acid, lauric acid, myristic acid, palmitic acid,
Saturated fatty acids such as stearic acid, arachidic acid, behenic acid, neo acids, side chain saturated fatty acids with a side chain in the α-position obtained by the oxo method, oleic acid, linoleic acid, linolenic acid, arachidonic acid, ricinoleic acid, etc. unsaturated fatty acids, succinic acid, adipic acid,
So-called dimer acids obtained by polymerizing dibasic carboxylic acids such as azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, their dibasic carboxylic acid anhydrides, and unsaturated fatty acids;
Examples include polymerized polybasic carboxylic acids consisting of trimer acids, trimellitic acids, and the like. These fatty acids can be used alone or in combination of two or more. In addition, as unsaturated fatty acids with 12-24 carbon atoms,
Typical examples include oleic acid, linoleic acid, linolenic acid, elaidic acid, ricinolenic acid, and ricinoelaidic acid.These fatty acids may be used as they are in the esterification reaction, but lower alkyl esters A transesterification reaction may also be carried out. In addition, thermal polymerization of esters with unsaturated double bonds obtained from (A), (B), and (C) and unsaturated fatty acids having 12 to 24 carbon atoms is carried out by conventional methods. The polymerization reaction of the present invention involves a complex relationship between the double bonds of ricinolenic acid in castor oil and the double bonds of unsaturated fatty acids reacted with it, and by controlling the reaction conditions, it can be used as rolling oil. It is possible to obtain a polymer that satisfies the necessary conditions. The reaction conditions for thermal polymerization are that the obtained ester or polyester is heated as it is at 200 to 300°C for 10 to 30 hours, and the progress of the reaction is usually checked by measuring the viscosity. In addition, the reaction temperature and time are selected depending on the desired viscosity, and the reaction conditions are controlled so that the viscosity of the obtained polymer falls within the range of 300 to 1800 cst (40°C). The polymer thus obtained is used as it is as a rolling oil and exhibits excellent performance. In addition, the polymer of the present invention includes animal and vegetable oils, mineral oils, antioxidants,
It can also be used in combination with a surfactant or the like. The present invention will be explained below using examples. Synthesis Example 1 935 parts of castor oil, 284 parts of stearic acid, and 12 parts of para-toluenesulfonic acid (hereinafter referred to as PTSA) were heated at 150-180°C under a stream of nitrogen gas (hereinafter referred to as _N2 gas).
The mixture was reacted for 6 hours to obtain an ester (ester-1) with an acid value of 1.0 and a hydroxyl value of 89.5. 423 parts of oleic acid and 16 parts of PTSA were added to this ester and reacted at 150-180°C for 8 hours to obtain a polyester having an acid value of 4.5, a hydroxyl value of 5.0, and a viscosity of 105cst (40°C). Furthermore, this polyester is 260−280
Thermal polymerization was carried out at ℃ for 20 hours to obtain a polymer having a viscosity of 700 cst (40 ℃). Synthesis Example 2 935 parts of castor oil, 733 parts of oleic acid, and 16 parts of PTSA were reacted at 150-160°C for 8 hours under a stream of _N2 gas.
An ester (Ester-2) having an acid value of 7.8, a hydroxyl value of 3.2, and a viscosity of 110 cst (40°C) was obtained. Subsequently, this ester was thermally polymerized at 260-270℃ for 20 hours, resulting in a viscosity of 1050cst.
(40°C) was obtained. Synthesis example 3 Castor oil with 30 moles of ethylene oxide added
2255 parts of oleic acid, 733 parts of oleic acid, and 30 parts of PTSA were reacted at 130-140°C for 6 hours under a _N2 gas stream to give an acid value of 6.5.
An ester (Ester-3) having a hydroxyl value of 4.8 and a viscosity of 102 cst (40°C) was obtained. Next, add this ester
Thermal polymerization at 220-230℃ for 15 hours, viscosity 620cst (40℃)
A polymer was obtained. Synthesis example 4 935 parts of castor oil, distilled rice bran fatty acid (iodine value
120) 564 parts and 15 parts of PTSA were heated under a stream of _N2 gas for 150−
React at 180°C for 6 hours, followed by maleic anhydride 18
The reaction was carried out at 100℃ for 2 hours and at 150-160℃ for 4 hours, resulting in an acid value of 1.8, a hydroxyl value of 4.5, and a viscosity of 380 cst (40
℃) polyester (ester-4) was obtained. Subsequently, this ester was further thermally polymerized at 260-270°C for 15 hours to obtain a polymer having a viscosity of 1350cst (40°C). Synthesis example 5 935 parts of castor oil, distilled rice bran fatty acid (iodine value
120) 738 parts and 12 parts of PTSA under _N2 gas flow,
Reacted at 150-180℃ for 6 hours, acid value 1.0, hydroxyl value
1.8, viscosity 100cst (40℃) ester (ester-
5) was obtained. Subsequently, this ester was thermally polymerized at 240-260°C for 15 hours to obtain a polymer having a viscosity of 800cst (40°C). Synthesis Example 6 3835 parts of castor oil with 50 moles of propylene oxide added, distilled rice bran fatty acid (iodine value 120) 733
and 45.5 parts of PTSA at 140-150℃ under _N2 gas flow.
Reacted for 7 hours, acid value 3.6, hydroxyl value 4.2, viscosity
An ester (ester-6) of 115 cst (40°C) was obtained. This ester was further heated at 240-260°C for 16 hours to carry out a thermal polymerization reaction to obtain a polymer having a viscosity of 750cst (40°C). Example No. 1-7 was prepared using the polymer of Synthesis Example 1-6 alone or as a blend as shown in Table 1, and a metal rolling oil lubrication performance test was conducted.

[Table] The friction coefficient (μ) and pressure resistance of Example No. 1-7 were measured, and the results are shown in Table-2. In addition, the rolling test was conducted by applying a fixed amount of Example No. 1-6 to the rolled material as it was, and by supplying Example No. 7 as a 15% emulsion. The amount of oil adhering to the rolled material was set to 1 g/m ² in all Examples Nos. 1-7. The test results are used to evaluate rolling performance based on the relationship between rolling reduction ratio (%) and rolling force (ton), and are shown in Figure-
Shown in 1. As a comparative example, commercially available tallow-based rolling oil was used. For the esters 1 to 6 obtained in Synthesis Examples 1 to 6, the friction coefficient, pressure resistance, and rolling load at a rolling reduction of 60% were measured using single samples as in the same manner as in the examples. The results are shown in Table 2 (Reference Example). 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 type pendulum type oil tester N-type load carrying capacity test method Shell type high speed four ball friction tester rolling test method Rolling mill: Four-roll rolling mill Work roll diameter 150mm Width 140mm Back-up roll diameter 250mm Width 140mm Roll material Chrome steel roll circumferential speed 30m/min Rolling material: SPC-C Thickness 0.60mm x Width 50mm x Length 150mm Method of measuring rolling performance Two rolls with a spacing of 50mm (l ₁ ) are placed 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 At that time, the rolling load (ton) was measured using a load cell.

[Table] Polymers obtained by thermally polymerizing castor oil or its derivatives obtained in the present invention as described above, or metal rolling oils using the same as base oil (Examples 1 to 3)
7) has a lower coefficient of friction than esters that do not undergo thermal polymerization (esters 1 to 6 in reference examples), has higher pressure resistance at high speed rotation, and has a lower rolling load, providing excellent lubricity and rolling performance. It shows.
From these results, a rolling oil with high oil film strength and suitability for high speeds was obtained, and by using this oil, rolling could be performed under high pressure and high speed, and rolled steel sheets could be manufactured with higher efficiency. Can be done.

[Brief explanation of the drawing]

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. Obtained by reacting (A) castor oil, (B) castor oil with alkylene oxide added, (C), (A) or (B) with a monocarboxylic acid or polycarboxylic acid having 4 to 60 carbon atoms. (A), (B), (C) of a partial ester in which at least one hydroxyl group remains in the molecule
At least one species selected from group 3 and carbon number 12
A metal rolling oil characterized by using a polymer obtained by thermally polymerizing a reaction product obtained by carrying out an esterification reaction with a -24 unsaturated fatty acid.