JPS6326159B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metal rolling oil suitable for high-pressure, high-speed rolling. Conventionally, commonly used rolling oils include oil-based rolling oils that use palm oil, beef tallow, lard, whale oil, etc. as base oils, mineral oil-based rolling oils, and rolling oils that are a mixture of animal and vegetable oils and mineral oils. All of these are widely used as base oils such as animal and vegetable oils, petroleum hydrocarbons, etc., to which oiliness improvers, extreme pressure additives, antioxidants, surfactants, etc. are added. However, with the rapid advancement of rolling machinery equipment, rolling at higher pressures and higher speeds is required.
In addition, as the rolling process, the number of passes, and the conditions for rolling oil are becoming more severe year by year, the performance of conventional rolling oil is not necessarily sufficient to meet these demands. At present, no rolling oil has been found to replace these. Therefore, the present invention provides a rolling oil that has superior lubrication performance than conventional rolling oils and can sufficiently cope with the current high-pressure, high-speed rolling processes and even more severe rolling processes expected in the future. That is. The metal rolling oil of the present invention is obtained by polymerizing a polyhydric alcohol or a polyhydric alcohol to which an alkylene oxide has been added, and (A) a saturated fatty acid or unsaturated fatty acid having a total of 12 to 22 carbon atoms, or the unsaturated fatty acid. Polymerized fatty acid (B) in which at least one carboxyl group in the molecule forms an ester with a hydroxy compound having an alkyl group or an alkenyl group having 12 to 18 carbon atoms, and at least one carboxyl group remains. A partial ester with at least one hydroxyl group remaining in the molecule, which is obtained by reacting a polycarboxylic acid partial ester with at least one selected from the group (A) and (B). and at least one member selected from the group of dicarboxylic acids, phosphoric acid or phosphoric anhydride, epoxy compounds, and isocyanate compounds, which have at least two functional groups in the molecule that can react with the hydroxyl groups. It is a metal rolling oil characterized by using at least one type of compound or its salt, and it can also be used by adding extreme pressure additives, surfactants, antioxidants, etc. as necessary. It is. Polyhydric alcohols in the present invention include, for example, glycerin, polyglycerin, pentaerythritol, sorbitol, sucrose, trimethylolpropane, etc., and examples of alkylene oxides to be added to these polyhydric alcohols include ethylene oxide, propylene oxide, butylene oxide, etc. These include oxides, etc., and these may be added only one type, or two or more types may be added randomly or in blocks, and the number of moles added is 2.
-100, preferably 3-30 mol. On the other hand, the carboxyl compounds (A) and (B) that form a partial ester with the polyhydric alcohol or the polyhydric alcohol added with alkylene oxide include (A) lauric acid, myristic acid, palmitic acid,
Saturated fatty acids such as stearic acid, arachidic acid, and behenic acid; side chain saturated fatty acids such as fatty acids obtained by the oxo method; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, and ricinoleic acid; (B) at least one selected from polymerized fatty acids such as dimer acid and trimer acid obtained by polymerizing fatty acids; basic carboxylic acids and their acid anhydrides,
Furthermore, polymerized fatty acids consisting of dimer acid and trimer acid obtained by polymerizing the unsaturated fatty acids mentioned in (A) above, and polycarboxylic acids such as trimellitic acid, lauryl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, Oleyl alcohol, ethylene glycol oleate, propylene glycol laurate, propylene glycol stearate, polyethylene glycol palmitate, polyethylene glycol oleate, glycence stearate, sorbitol laurate, sorbitol oleate, pentaerythritol stearate, etc., and their alkylenes Examples include compounds such as esters obtained from hydroxy compounds such as oxide adducts, and the above carboxyl compound (B) is a combination of at least one alkyl group having 12 to 18 carbon atoms or an alkenyl group and a carboxyl group of a polycarboxylic acid. It is an essential condition that at least one of the groups remains. These partial esters of at least one selected from carboxyl compounds (A) and (B) and a polyhydric alcohol or a polyhydric alcohol to which alkylene oxide has been added can be synthesized by a general method. It is also possible to synthesize by a transesterification method using a lower alkyl ester of a carboxyl compound, and the present invention is not limited in any way by these synthesis methods. However, the major feature of the present invention is that the above ester has at least one hydroxyl group remaining in one molecule,
With this polyfunctional compound that can react with hydroxyl groups,
It is formed by bonding two or more molecules of ester. The polyfunctional compounds in the present invention include, firstly, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid,
Dicarboxylic acids such as dimer acid, secondly phosphoric acid, phosphoric anhydride, thirdly ethylene glycol diglycidyl ether, glycerin triglycidyl ether, adipic acid diglycidyl ester, succinic acid diglycidyl ester, dimer acid diglycidyl ester, poly Polyvalent epoxy compounds such as alkylene glycol diglycidyl ether, triglycidyl ether of glycerin added with alkylene oxide, fourthly methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, nitrodiphenyl diisocyanate, nitrodiphenyl Isocyanate compounds such as methane diisocyanate, diphenylmethanesulfone diisocyanate, diphenylsulfone diisocyanate, naphthalene diisocyanate, fluorene diisocyanate, glycene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate The reaction between these polyfunctional compounds and the ester having at least one remaining hydroxyl group is carried out by a conventional method. The obtained reaction product is used after the residual acid radicals are neutralized with an inorganic alkali compound, an alkaline earth metal compound, an organic amine or a derivative thereof, etc., if necessary. By this neutralization, the hydrophilicity of the reaction product can be appropriately adjusted depending on the conditions of use, and the polarity of the reaction product can also be adjusted to control the adsorption to metal surfaces. These reaction products have high performance as rolling oil when used as is, but they can also be mixed with conventional rolling oil, animal or vegetable oils, mineral oils, or added with extreme pressure additives, antioxidants, surfactants, etc. Can be used. The present invention will be explained in more detail with reference to Examples below. Example 1 136 parts of pentaerythritol, 710 parts of stearic acid
A portion was reacted at 220 to 240°C for 6 hours under a nitrogen gas stream to obtain an ester having an acid value of 2.0 and a hydroxyl value of 95. Add to this 73 parts of adipic acid and 8 parts of para-toluenesulfonic acid.
The mixture was reacted at 160°C for 8 hours to obtain a polyester having an acid value of 2.04 and a hydroxyl value of 19.0. Example 2 136 parts of pentaerythritol, 710 parts of stearic acid
The mixture was reacted at 220 to 240°C for 6 hours under a nitrogen gas stream to obtain an ester having an acid value of 2.0 and a hydroxyl value of 95.
Next, 146 parts of adipic acid and 10 parts of para-toluenesulfonic acid were added to this and reacted at 160°C for 8 hours to obtain a polyester having an acid value of 2.0 and a hydroxyl value of 0.8. The pH of a 1% aqueous solution of this polyester in caustic potassium is 7.0.
After neutralization, it was dehydrated. Example 3 166 parts of diglycerin and 565 parts of oleic acid were reacted at 200 to 250°C for 5 hours under a nitrogen gas stream,
An ester with an acid value of 0.62 and a hydroxyl value of 154 was obtained. Next, 250 parts of 4,4'-diphenylmethane diisocyanate and 2 parts of triethylenediamine were added to this ester at 120°C. The product obtained has an acid value
It is a polycarbamate ester with a hydroxyl value of 0.18 and a hydroxyl value of 5.6. Example 4 106 parts of trimethylolpropane and 680 parts of behenic acid were reacted under a nitrogen gas stream at 240 to 250°C for 8 hours to obtain an ester with an acid value of 2.14 and a hydroxyl value of 72. By adding 83 parts of ethylene glycol diglycidyl ether and 2 parts of boron trifluoride etherate to this ester and reacting at 80°C for 6 hours, the acid value
A polyester polyol with a hydroxyl value of 0.85 and a hydroxyl value of 60 was obtained. Example 5 182 parts of sorbitol and 568 parts of stearic acid were reacted at 160°C for 2 hours under a nitrogen gas stream, and then further reacted with 200 parts of stearic acid.
Reacted at ~240℃ for 5 hours, acid value 4.5, hydroxyl value 160
The ester was obtained. This ester contains phosphoric anhydride.
Add 142 parts at 60-70℃, acid value 130, hydroxyl value 32
of polyester was obtained. This product was neutralized with caustic soda and the pH of the 1% solution was adjusted to 7.0. Example 6 136 parts of pentaerythritol, 568 parts of stearic acid
282 parts of dimer acid under nitrogen gas stream 200 ~
The reaction was carried out at 240°C for 12 hours to obtain a polyester having an acid value of 1.64 and a hydroxyl value of 56. Next, 83 parts of ethylene glycol diglycidyl ether and 2 parts of boron trifluoride etherate were added and reacted at 80 to 100°C for 4 hours.
A polyester polyol having an acid value of 0.80 and a hydroxyl value of 51 was obtained. Example 7 624 parts of stearic acid diglyceride and 100 parts of succinic anhydride were reacted at 100 to 110°C for 4 hours under a nitrogen gas stream to obtain stearic acid diglyceride succinate. Next, 106 parts of trimethylolpropane was added and the reaction was carried out for 10 hours at 200 to 240 ℃ under a nitrogen gas stream to obtain an ester with an acid value of 2.4 and a hydroxyl value of 127. The above ester was maintained at 70-80°C, 71 parts of phosphoric anhydride was added, and after the addition was completed, an additional 4 parts was added at 70-80°C.
The reaction was continued for hours to obtain a polyester with an acid value of 115 and a hydroxyl value of 24. As a result of neutralizing this polyester with caustic soda, the pH of the 1% aqueous solution was 7.0. Example 8 694 parts of polyoxyethylene diglycerin ether (12 mole ethylene oxide adduct), 282 parts of oleic acid, 282 parts of dimer acid, and 286 parts of monolauryl succinate were mixed at 200 to 240°C under a nitrogen gas stream for 15 minutes.
A dehydration reaction was carried out for a period of time to obtain an ester with an acid value of 1.9 and a hydroxyl value of 35. Next, 66 parts of adipic acid and 8 parts of para-toluenesulfonic acid were added, and the mixture was heated at 160 to 180°C.
After a time reaction, a polyester having an acid value of 3.0 and a hydroxyl value of 5.0 was obtained. Example 9 518 parts of polyoxyethylene diglycerin ether (8 moles of ethylene oxide adduct), 572 parts of monolauryl succinate, and 3 parts of sulfuric acid were reacted at 160 to 180°C for 4 hours under a nitrogen gas stream, resulting in an acid value of 3.0 and a hydroxyl group. An ester with a value of 105 was obtained. 70 this ester
The temperature was maintained at ~80°C and 71 parts of phosphoric anhydride was added. After the addition was completed, the reaction was further carried out at 70 to 80°C for 4 hours to obtain a polyester having an acid value of 30 and a hydroxyl value of 25. Example 10 518 parts of polyoxyethylene diglycerin ether (8 moles of ethylene oxide adduct), 572 parts of monolauryl succinate, and 3 parts of sulfuric acid were reacted at 160 to 180°C for 4 hours under a nitrogen gas stream to give an acid value of 3.0 and a hydroxyl group. An ester with a value of 105 was obtained. 174 parts of ethylene glycol diglycidyl ether was added to this ester and reacted at 80 to 100°C for 4 hours to obtain a polyester polyode having an acid value of 0.8 and a hydroxyl value of 85. The friction coefficient (μ) and pressure resistance of rolling oils No. 1 to 11 with the composition shown in Table 1 using the compounds obtained in Examples 1 to 10 were measured, and the results were used as a comparative example to measure the rolling oil No. 1 to 11 of the compositions shown in Table 1. The results are shown in Table 2 along with the measurement results of rolling oil. In addition, in the rolling performance test, a fixed amount of rolling oil Nos. 1 to 10 was directly applied to the rolled material, and No. 11 was applied directly to the rolled material.
The amount of oil adhering to the rolled material was tested by supplying it as a 15% emulsion, and the amount of oil adhering to the rolled material was No.
No. 1 to No. 11 were all set to 1 g/m ² . The test results are shown in Figure 1, where rolling performance was evaluated based on the relationship between rolling reduction ratio (%) and rolling force (ton). In addition, as a comparative example, a commercially available tallow-based rolling oil was used. 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 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 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 x Width 50mm x Length 150mm Method for measuring rolling performance 50mm spacing between steel plates before rolling (l ₁ ) Two lines were drawn, the lines were rolled, the distance (l ₂ ) after rolling was measured, and the rolling reduction was determined using the following formula. Rolling ratio (%)=l ₂ −l ₂ /l ₂ ×100 Further, the rolling load (ton) at that time was measured using a load cell.

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【table】 [Brief explanation of drawings]

FIG. 1 is a rolling performance comparison chart showing the rolling performance of the rolling oils Nos. 1 to 11 of the present invention and the comparative example in terms of the relationship between rolling load and rolling reduction.

Claims (1)

[Scope of Claims] 1. A polyhydric alcohol or a polyhydric alcohol added with an alkylene oxide, and (A) a saturated fatty acid or unsaturated fatty acid having a total of 12 to 22 carbon atoms, or a polymer obtained by polymerizing the unsaturated fatty acid. Fatty acid (B) A polyester in which at least one carboxyl group in the molecule forms an ester with a hydroxy compound having an alkyl group or an alkenyl group having 12 to 18 carbon atoms, and at least one carboxyl group remains. A partial ester with at least one hydroxyl group remaining in its molecule, which is obtained by reacting at least one carboxylic acid partial ester selected from the group (A) and (B); A compound obtained by reacting with at least one selected from the group of dicarboxylic acids, phosphoric acid or phosphoric anhydride, epoxy compounds, and isocyanate compounds, which have at least two functional groups in the molecule that can react with hydroxyl groups. A metal rolling oil characterized by using at least one kind of or a salt thereof.