JPH027354B2 - - 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 compound obtained by cross-linking a partial ester of polyhydric alcohol or an alkylene oxide adduct of polyhydric alcohol 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. drawing, wire drawing,
In metal processing such as cutting, grinding, and pressing, metal rolling supplies rolling oil to the biting part between the rolled material and the roll, and forcibly draws the rolling oil into the lubricating part by the movement of the rolled material and the rotation of the roll. Although machining is performed using fluid lubrication, fluid lubrication is also performed.
Extreme-pressure lubrication or boundary lubrication is performed because extremely high pressure is applied to a portion or a new surface of metal is generated. In particular, in cutting and grinding processes, high pressure is applied locally and a large amount of new surfaces are generated at high speeds, so it is impossible to perform the process with fluid lubrication alone, and extreme pressure lubrication is important, so a large amount of extreme pressure addition is required. agent is added. 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. A polyhydric alcohol or a polyhydric alcohol to which an alkylene oxide has been added, (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) in the molecule. (A) of a dicarboxylic acid partial ester in which at least one carboxyl group forms an ester with a hydroxy compound having an alkyl group having 12 to 18 carbon atoms or an alkenyl group, and in which at least one carboxyl group remains. , a partial ester having at least one hydroxyl group remaining in its molecule, which is obtained by reacting at least one member selected from the group of , (B), and a functional group capable of reacting with the hydroxyl group. A compound obtained by reacting with 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 molecules in the molecule, or a salt thereof A lubricant for metal processing used in drawing, wire drawing, cutting, grinding, and press processing, characterized by using at least one of the above. Polyhydric alcohols in the present invention include, for example, glycerin, polyglycerin, pentaerythritol, sorbitol, sucrose, trimethylolpropane, etc., and alkylene oxides to be added to these polyhydric alcohols include, for example, ethylene oxide, propylene oxide, etc. These may be added alone, or two or more may be added randomly or in blocks, and the number of moles added is 2 to 100, preferably 3 to 30. be. 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, 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. Hydroxy compounds 1 such as laurate, propylene glycol stearate, polyethylene glycol palmitate, polyethylene glycol oleate, glycerin stearate, sorbitol oleate, pentaerythritol stearate, and alkylene oxide adducts thereof
The above-mentioned dicarboxylic acid partial ester (B) has at least one alkyl group or alkenyl group having 12 to 18 carbon atoms in its molecule, It is an essential condition that one carboxyl group of the dicarboxylic acid remains. These partial esters of at least one of the carboxyl compounds (A) and (B) and a polyhydric alcohol or a polyhydric alcohol to which an alkylene oxide has been added can be synthesized by a general method, but the carboxyl compound It is also possible to synthesize by a transesterification method using a lower alkyl ester of , 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-mentioned ester has at least one hydroxyl group remaining in one molecule, and two or more molecules of ester are bonded together using a polyfunctional compound that can react with this hydroxyl group. It is what happens. 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, glycentriglycidyl ether, adipic acid diglycidyl ester, succinic acid diglycidyl ester, dimer acid diglycidyl ester, polyalkylene glycol diglycidyl ether, triglycidyl ether of glycerin added with alkylene oxide. Polyvalent epoxy compounds such as methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, nitrodiphenyl diisocyanate, nitrodiphenylmethane diisocyanate, diphenylmethane sulfon diisocyanate, diphenyl sulfon diisocyanate, Examples include polyvalent isocyanate compounds such as naphthalene diisocyanate, fluorene diisocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate, and these polyfunctional compounds and at least one hydroxyl group. Reactions with the remaining esters are carried out in a conventional manner. 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 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 in combination with animal and vegetable oils, mineral oils, extreme pressure additives, antioxidants, surfactants, and the like. 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. Next, 73 parts of adipic acid, 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 2.0 and a hydroxyl value of 19.0. Example 2 136 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. Next, 146 parts of adipic acid, para-toluenesulfonic acid
10 parts were added and reacted at 160°C for 8 hours to obtain a polyester having an acid value of 20 and a hydroxyl value of 0.8. This polyester was neutralized with caustic potassium so that the pH of a 1% aqueous solution was 7.0, and then 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 0.6 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.
It was added at 120°C. The obtained product has an acid value of 0.2,
It is a polycarbamate ester with 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 having an acid value of 2.1 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
Dimer acid obtained by polymerizing oleic acid
282 parts were reacted for 12 hours at 200 to 240°C under a nitrogen gas stream to obtain a polyester having an acid value of 1.6 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 to obtain a polyester polyol having an acid value of 0.8 and a hydroxyl value of 51. 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. Then trimethylolpropane 106
The reaction was carried out at 200 to 240°C for 10 hours under a nitrogen gas stream to obtain an ester having an acid value of 2.4 and a hydroxyl value of 127. The above ester was maintained at 70 to 80°C, 71 parts of phosphoric anhydride was added, and after the addition was completed, the reaction was continued for another 4 hours at 70 to 80°C to obtain a polyester having an acid value of 115 and a hydroxyl value of 24. As a result of neutralizing this polyester with caustic soda, the pH of its 1% aqueous solution was 7.0.
It was hot. Example 8 314 parts of adipic acid monolaurate, 396 parts of adipic acid monooleate, and 166 parts of diglycerin were reacted for 16 hours at 200 to 240°C under a nitrogen gas stream, resulting in an acid value of 1.2,
An ester with a hydroxyl value of 123.0 was obtained. 98 parts of maleic anhydride and 9 parts of para-toluenesulfonic acid were added to the above ester and reacted at 160°C for 10 hours to obtain a polyester having an acid value of 2.1 and a hydroxyl value of 4.3. Example 9 694 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 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. 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 11 518 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. 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 polyol having an acid value of 0.8 and a hydroxyl value of 85. Example 12 396 parts of adipic acid monooleate, 284 parts of stearic acid and 382 parts of polyoxypropylene glycerin ether (5 mole propylene oxide adduct),
12 parts of paratoluenesulfonic acid under nitrogen gas flow
Reacted at 200-220℃ for 12 hours, acid value 2.1, hydroxyl value
49.8 esters were obtained. This ester contains 3 parts of triethylene diamine and naphthalene diisocyanate.
Add 105 parts of
0.6, and an ester with a hydroxyl value of 3.6 was obtained. As a lubricating performance test of the ester compounds of Examples 1 to 12, friction coefficient (μ), pressure resistance (seizure load), ring compression test, drawing test, cutting 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] 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: S20C ring material with outer diameter of 20 mm x inner diameter of 10 mm x height of 5 mm Sample: Compound measurement results of Examples 3, 5, 6, and 7 are shown in Table 2. .

[Table] 3. Pulling test A drawing test was conducted under the following conditions, and the results are shown in Table 3 in terms of pull-out 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 3: 〃 =〃; 〃 Compound of Example 4: 〃 =〃; 〃 Johnson JP105: 〃 =〃; The pull-out resistance and number of seizures were measured. Dice temperature: 100℃

[Table] 4 Cutting test A cutting test was conducted under the following conditions, and the results were calculated based on 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 SAE 51-416F Cutting tool: SKH-4B Oil flow rate: 1/min Judgment: Number of cutting materials that can be cut with one cutting tool Sample: The compounds of Examples 5, 10, 11, and 12 were mixed as cutting oils as follows. Blend A Compound 60 spindle oil emulsifier of Example 5 30 parts 60 parts 10 parts Blend B Compound 60 spindle oil emulsifier of Example 10 30 parts 60 parts 10 parts Blend C Compound 60 spindle of Example 11 Oil emulsifier 30 parts 65 parts 5 parts Compound D Example 12 Compound 60 spindle oil emulsifier 30 parts 65 parts 5 parts Commercially available product Shoseki cutlet soluble oil Compounds A, B, C, D and commercially available The product was 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: Aluminum ultra-fine wire with a diameter of 30μ Judgment: Measure the number of wire breaks due to entanglement when drawing an aluminum ultra-fine wire with a diameter of 30μ into an ultra-fine wire with a diameter of 25μ Sample: Examples 1, 8, and 9 of the present invention , 12 compounds were mixed as follows. Blend E Compound 60 spindle oil of Example 1 10 parts 90 parts Blend F Compound 60 spindle oil of Example 8 10 parts 90 parts Blend G Compound 60 spindle oil of Example 9 10 parts 90 parts Blend H Example 12 compounds 60 spindle oil 10 parts 90 parts Combination product I Jiyeonson JP105 60 spindle oil 10 parts 90 parts

【table】

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 dicarboxylic compound 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 acid partial ester selected from the group (A) and (B), and the hydroxyl group. obtained by reacting with at least one 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 A lubricant for metal processing used in drawing, wire drawing, cutting, grinding, and press processing, characterized in that it uses at least one type of compound of the form or a salt thereof.