JPH028637B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a lubricant used in metal processing other than rolling, such as drawing, wire drawing, cutting, grinding, and pressing. Metal processing oils such as drawing oils, wire drawing oils, cutting oils, grinding oils, and press oils are generally animal and vegetable oils, mineral oils, or mixtures thereof, with oiliness improvers, extreme pressure additives, rust preventives, and oxidation agents. Add inhibitors, emulsifiers, etc.
It is used as it is or as a 1 to 30% emulsion, but as processing machines become larger and more precise,
In addition, processing conditions are becoming increasingly harsh, such as increased hardness of metal materials, higher speeds and higher pressures, and more precise finished surfaces.Currently, conventional lubricants cannot be used. However, it has become impossible to use them under these harsh conditions. In other words, there is a growing demand for the development of even higher performance lubricants. The present inventors conducted intensive research focusing on these points, developed castor oil esters or derivatives thereof, found that they were excellent as metal rolling oils, and filed a patent application. Kosho 52-20430,
(Japanese Patent Application Laid-open No. 55-110192). Subsequently, as a result of continuing research on these, a crosslinked compound of a partial ester of polyhydric alcohol and a carboxy compound with alkylene oxide added was found to be used in metal processing such as drawing, wire drawing, cutting, grinding, pressing, etc. excluding rolling. It was discovered that it has excellent performance as a lubricant. i.e. pulling out,
In metal processing such as wire drawing, cutting, grinding, and pressing, metal rolling supplies rolling oil to the biting part between the rolled material and the roll, and forcibly lubricates the rolling oil by moving the rolled material and rotating the roll. In contrast, fluid lubrication is also used, but extreme pressure lubrication or boundary lubrication is performed because extremely high pressure is applied to a part or a new surface of metal is generated. ing. In particular, in cutting and grinding processes, high pressure is applied locally and new surfaces are generated at high speeds, so it is impossible to perform the process with fluid lubrication alone, and extreme pressure lubrication is required, so a large amount of depressurizing additives are added. It is being In addition, high pressure is applied to the parts that are deformed in press working and drawing processes, and fluid lubrication alone cannot perform quick and accurate processing, making it necessary to add extreme pressure additives. As mentioned above, metal processing such as drawing, wire drawing, cutting, grinding, and pressing requires different performance from rolling processing, and as a result of studying lubricants that can be used for these processing, we came up with the invention of the present application. be. The compound of the present invention consists of the following. That is, a polyhydric alcohol, (A) a saturated fatty acid or an unsaturated fatty acid having a total of 12 to 22 carbon atoms, or a polymerized fatty acid obtained by polymerizing the unsaturated fatty acid, and (B) at least one carboxyl group in the molecule. (A) and (B) groups of dicarboxylic acid partial esters which form 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. An addition reaction product obtained by adding an alkylene oxide to a partial ester having at least one hydroxyl group remaining in its molecule, which is obtained by reacting with at least one selected from A compound selected from the group of dicarboxylic acids, phosphoric acid or phosphoric anhydride, polyvalent epoxy compounds, and polyvalent isocyanate compounds, which have at least two functional groups in the molecule that can react with the hydroxyl groups (referred to as "AO adducts"). For metal processing used in drawing, wire drawing, cutting, grinding, and press processing, characterized by using at least one compound obtained by reacting with at least one compound, or a salt thereof. It is a lubricant. Examples of the polyhydric alcohol in the present invention include glycerin, polyglycerin, pentaerythritol, sorbitol, sucrose, and trimethylolpropane. On the other hand, the carboxyl compounds (A) and (B) that form partial esters with the polyhydric alcohol 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, 1 mole of dicarboxylic acid such as dimer acid obtained by polymerizing the unsaturated fatty acids mentioned in (A) above, lauryl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, ethylene glycol oleate, propylene glycol. obtained by reacting 1 mol of a hydroxy compound such as laurate, propylene glycol stearate, polyethylene glycol palmitate, polyethylene glycol oleate, glycerin stearate, sorbitol oleate, pentaerythritol stearate, etc. and their alkylene oxide adducts. The dicarboxylic acid partial ester (B) has at least one alkyl group or alkenyl group having 12 to 18 carbon atoms in its molecule, and It is an essential condition that one carboxyl group remains. These partial esters of at least one of the carboxy compounds (A) and (B) and a polyhydric alcohol can be synthesized by a general esterification reaction, but using a lower alkyl ester of a carboxyl compound, It is also possible to synthesize by transesterification, and the present invention is not limited in any way by these synthesis methods. Next, an alkylene oxide is added to the above partial ester to obtain an AO adduct. Examples of alkylene oxides that react with the hydroxyl groups remaining in the partial ester of the polyhydric alcohol include ethylene oxide and propylene oxide.
The species may be added randomly or in blocks, and the number of moles added (if two species are added, the total) is 2 to 100 moles, preferably 3 to 60 moles. A major feature of the present invention is that two or more molecules of the AO adduct are bonded by a polyfunctional compound capable of reacting with a hydroxyl group. The polyfunctional compounds used in the present invention include firstly dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, and dimer acid, and secondly phosphoric acid and phosphoric anhydride. , thirdly ethylene glycol diglycidyl ether, glycerin triglycidyl ether,
Polyvalent epoxy compounds such as adipic acid diglycidyl ester, succinic acid diglycidyl ester, dimer acid diglycidyl ester, polyalkylene glycol diglycidyl ether, triglycidyl ether of glycerin with alkylene oxide added, fourthly, methylene diisocyanate, tolylene dihydride, etc. Isocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, nitrodiphenyl diisocyanate, nitrodiphenylmethane diisocyanate, diphenylmethane sulfone diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, fluorene diisocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, bifu Examples include polyvalent isocyanate compounds such as enyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate, and these polyfunctional compounds,
The reaction with the AO adduct is carried out in a conventional manner.
The resulting reaction product can be used to remove residual acid groups as needed.
It is used after being neutralized with inorganic alkali compounds, alkaline earth metal compounds, organic amines, derivatives, etc. 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 can be used as they are as lubricants for metal processing such as drawing, wire drawing, cutting, grinding, and press processing, and have extremely high lubricating performance, but if necessary, they can be used with other lubricants, Alternatively, it can be used by mixing with animal and vegetable oils, mineral oils, extreme pressure additives, antioxidants, surfactants, etc. 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
After reacting for 6 hours at 200 to 240°C under a nitrogen gas stream, 440 parts of ethylene oxide was added at 160 to 180°C using 2 parts of potassium hydroxide as a catalyst to give an acid value of 1.7.
An AO adduct with a hydroxyl value of 43.6 was obtained. 73 parts of adipic acid and 8 parts of para-toluenesulfonic acid were added to this AO adduct and reacted at 160°C for 8 hours to obtain a compound with an acid value of 2.0 and a hydroxyl value of 10.0. Example 2 After reacting 166 parts of diglycerin and 565 parts of oleic acid at 200 to 250°C under a nitrogen gas stream for 5 hours, 1160 parts of propylene oxide was added at 160 to 180°C using 1.5 parts of potassium hydroxide as a catalyst. , an AO adduct with an acid value of 0.8 and a hydroxyl value of 60.5 was obtained. Next, 5 parts of triethylene diamine and 250 parts of 4.4'-diphenylmethane diisocyanate were added at 120°C, and after the addition was completed,
The reaction was carried out at 80-90°C for 4 hours. The obtained compound had an acid value of 0.2 and a hydroxyl value of 4.5. Example 3 After reacting 106 parts of trimethylolpropane and 680 parts of behenic acid at 240 to 250°C under a nitrogen gas stream for 8 hours, 1.6 parts of potassium hydroxide was added as a catalyst and 160 parts of behenic acid was reacted.
Add 220 parts of ethylene oxide at ~180℃ to reduce the acid value.
2.2, an AO adduct with a hydroxyl value of 56.0 was obtained. Next, 83 parts of ethylene glycol diglycidyl ether and 2 parts of boron trifluoride etherate were added and reacted at 80°C for 6 hours to obtain a compound with an acid value of 1.2 and a hydroxyl value of 46.7. Example 4 After reacting 182 parts of sorbitol and 568 parts of stearic acid at 160°C under a nitrogen gas stream for 2 hours,
After reacting at 240°C for 5 hours, 1.5 parts of potassium hydroxide was added as a catalyst, and 2200 parts of ethylene oxide was added at 160 to 180°C to give an acid value of 2.0 and a hydroxyl value of 76.1.
The AO adduct of was obtained. Add 42.6 parts of phosphoric anhydride to this.
It was added at 60 to 70°C to obtain a compound with an acid value of 40 parts and a hydroxyl value of 15.3. This product was further neutralized with sodium hydroxide. Example 5 136 parts of pentaerythritol, 568 parts of stearic acid
dimer acid obtained by polymerizing part and oleic acid
After reacting 282 parts at 200 to 240°C under a nitrogen gas stream for 12 hours, 1160 parts of propylene oxide was added at 180 to 190°C using 2 parts of potassium hydroxide as a catalyst to give an acid value of 1.2 and a hydroxyl value of 26.7. AO adduct was obtained. Next, 41.5 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 to obtain a compound with an acid value of 0.6 and a hydroxyl value of 24.6. Example 6 624 parts of stearic acid diglyceride was reacted with 100 parts of succinic anhydride at 100 to 110°C under a nitrogen gas stream for 4 hours, then 106 parts of trimethylolpropane was added, and the reaction was continued at 200 to 240°C for 10 hours. I went. Next, add 1.7 parts of potassium hydroxide as a catalyst and
Add 880 parts of ethylene oxide at 180℃ to reduce the acid value.
1.8, and an AO adduct with a hydroxyl value of 33.0 was obtained. The above AO adduct was maintained at 70-80°C, 47 parts of phosphoric anhydride was added, and after the addition was completed, an additional 4 parts of phosphoric acid was added at 70-80°C.
The reaction was continued for hours to obtain a compound with an acid value of 55 and a hydroxyl value of 12.0. This was neutralized with sodium hydroxide. Example 7 After reacting 314 parts of adipic acid monolaurate, 398 parts of adipic acid monostearate, and 166 parts of diglycerin at 200 to 220°C under a nitrogen gas stream for 12 hours, 2.1 parts of potassium hydroxide was added as a catalyst, and 170 parts of potassium hydroxide was added as a catalyst. ~180
Add 290 parts of propylene oxide at °C to determine the acid value.
0.9, and an AO adduct with a hydroxyl value of 95.1 was obtained. 2.5 parts of triethylenediamine was added to this, and 150 parts of tolylene diisocyanate was added and reacted at 100 to 110°C to obtain a compound having an acid value of 1.7 and a hydroxyl value of 6.4. Example 8 452 parts of sebacic acid monooleate, glycerin
After reacting 92 parts of para-toluenesulfonic acid with 6 parts of paratoluene sulfonic acid at 180 to 200°C for 10 hours under a nitrogen gas flow, 1.2 parts of potassium hydroxide was added, and 176 parts of ethylene oxide was added thereto at 170 to 180°C, resulting in an acid value of 1.6. Hydroxyl value 156.1
The AO adduct of was obtained. Next, add 98 parts of maleic anhydride and heat to 140-150°C.
The reaction was carried out for 6 hours to obtain a compound with an acid value of 1.5 and a hydroxyl value of 10. Example 9 After reacting 182 parts of sorbitol and 564 parts of oleic acid at 160°C under a nitrogen gas stream for 2 hours, 1 part of potassium hydroxide was added, and ethylene oxide was reacted at 180 to 190°C.
440 parts and 290 parts of propylene oxide were subjected to an addition reaction to obtain an AO adduct with an acid value of 0.4 and a hydroxyl value of 152. This is then added with adipic acid diglycidyl ester.
Add 260 parts and 2 parts of boron trifluoride etherate,
React at 80-100℃ for 4 hours, acid value 0.2, hydroxyl value
105 compounds were obtained. Example 10 136 parts of pentaerythritol and 628 parts of adipic acid monolaurate were heated at 200 to 220°C under a nitrogen gas stream.
After reacting for 10 hours, potassium hydroxide 2 was added as a catalyst.
propylene oxide at 180-190℃ using
580 parts were added to obtain an AO adduct with an acid value of 0.6 and a hydroxyl value of 122.1. Next, 174 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 to determine the acid value.
0.6, and a compound with a hydroxyl value of 110.3 was obtained. As a lubricating performance test of the ester compounds of Examples 1 to 10, friction coefficient (μ), pressure resistance (seizure load) ring compression test, drawing test, and wire drawing test were conducted. (1) Friction coefficient (μ) is measured using Soda pendulum type oil tester.
The pressure resistance (seizure load) of the N2 type was measured using a Schiel high-speed four-ball friction tester. The results are shown in Table-1.

【table】

[Table] (2) Ring compression test A ring compression test was conducted under the following conditions, and the results are shown using the friction coefficient. Testing machine: Universal material testing machine Compression load: 80t Compression material: Ring material of 20 mm outer diameter x 10 mm inner diameter x 5 mm height S20C Sample: Compounds of Examples 1, 2, 3, and 4 The measurement results are shown in Table-2.

[Table] (3) Drawing test A drawing test was conducted under the following conditions, and the results are shown in Table 3 in terms of the pulling load and number of seizures. Testing machine: Draw bench Drawing speed: 1 m/min Drawing material: S45-C diameter 7 mm x length 1000 mm Sample: Compound of Example 1: Machine oil = 50 parts; 50 parts Compound of Example 2: 〃 =〃; Compound of Example 4: 〃 =〃; 〃 Compound of Example 9: 〃 =〃; 〃 Compound of Example 10: 〃 =〃; 〃 Johnsson JP105: 〃 =〃;
(Commercial product) Judgment method The pull-out resistance and number of seizures were measured when a steel material with a diameter of 7.0 mm was changed to a steel material with a diameter of 5.8 mm. Dice temperature: 100℃

[Table] (4) Cutting test A cutting test was conducted under the following conditions, and the results were expressed as the number of cutting materials that could be cut per tool.
It is shown in Table-4. Cutting speed: 70m/min Machining speed: 8μ/min Cutting material: Free-cutting stainless steel SAE51-416F Cutting tool: SKH-4B Oil flow rate: 1/min Judgment: Judgment based on the number of cutting materials that can be cut with one cutting tool Sample: The compounds of Examples 5, 6, 7, and 8 were blended as cutting oils as follows. Compound A Compound 60 of Example 5 Spindle oil emulsifier 30 parts 60 parts 10 parts Compound B Compound 60 spindle oil emulsifier of Example 6 30 parts 60 parts 10 parts Compound C Compound 60 of Example 7 Spindle oil emulsifier 30 parts 65 parts 5 parts Compound D Compound 60 spindle oil emulsifier of Example 8 30 parts 65 parts 5 parts Commercial product Shoseki cutlet soluble oil Mixtures A, B, C, D and the commercial product were diluted 10 times with water. , and subjected to a cutting test.

[Table] (5) Wire drawing test A wire drawing test was conducted under the following conditions, and the results are shown in Table 5 in terms of the number of wire breaks. Wire drawing material: 30μ diameter aluminum ultrafine wire Judgment: 30μ diameter aluminum ultrafine wire
Measurement of the number of wire breaks due to entrainment when drawing a 25 μm ultrafine wire Sample: The compounds of Examples 1, 3, 5, and 9 of the present invention were blended as follows. Compound E Compound 60 spindle oil of Example 1 10 parts 90 parts Compound F Compound 60 spindle oil of Example 3 10 parts 90 parts Compound G Compound 60 spindle oil of Example 5 10 parts 90 parts Compound H Example Compound 9 60 spindle oil 10 parts 90 parts Compound I Jiyeonson JP105 60 spindle oil 10 parts 90 parts

【table】

Claims (1)

[Scope of Claims] 1. A polyhydric alcohol, (A) a saturated fatty acid or an unsaturated fatty acid having a total of 12 to 22 carbon atoms, or a polymerized fatty acid obtained by polymerizing the unsaturated fatty acid (B) at least in the molecule. (A) of a dicarboxylic acid partial ester in which one carboxyl group 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; An addition reaction product obtained by adding an alkylene oxide to a partial ester with at least one hydroxyl group remaining in its molecule, which is obtained by reacting with at least one member selected from the group (B). and at least one selected from the group of dicarboxylic acids, phosphoric acid or phosphoric anhydride, polyvalent epoxy compounds, and polyvalent isocyanate compounds having at least two functional groups in the molecule that can react with the hydroxyl groups.
A lubricant for metal working used in drawing, wire drawing, cutting, grinding, and press working, characterized by using at least one compound obtained by reacting with a seed, or a salt thereof.