JPH0437117B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metal processing composition, more specifically, a water-soluble composition having a basic nitrogen atom or a cationic nitrogen atom whose counter anion is a phosphorus oxygen acid, and having an average molecular weight of 500 or more and less than 1000. The present invention relates to a metal processing composition containing a cationic compound. Conventionally, lubricants used for metal machining, such as rolling, drawing, cutting, and grinding, are based on animal and vegetable oils, mineral oils, etc., and fatty acids, alcohols, etc. are added as oily agents, and extreme pressure The composition contains organic phosphorus compounds, organic chlorine compounds, etc. as additives, and further emulsifiers as necessary, and these components provide lubrication under various frictional conditions that occur between the tool and the workpiece. Designed to be effective. Among the basic compositions mentioned above, the oily agent has a large effect on the lubricating performance, and as this oily agent, fatty acids having about 8 to 20 carbon atoms, their dimer acids, and their salts have conventionally been used. Fatty acids have traditionally been widely used during metal processing because they react with the respective metals on the surfaces of tools and workpieces, strongly adsorbing and arranging them on the metal surfaces, and exhibiting good lubricity. Naturally, it also reacts with the generated wear metal powder, producing metal soap that easily disappears from the lubricating fluid. As a result, there is a problem in that the lubrication performance changes over time, which impedes work stability. Furthermore, the generated metal soap impairs the stability of the lubricating liquid, often making the liquid unusable. In addition, the heat and shearing forces generated during metal processing cause partial deterioration, which accelerates the deterioration of the oil that floats to the surface, significantly contaminating processed products and processing machines, and requiring a large amount of expense to clean them. do. In order to avoid the various problems caused by the use of fatty acid-based oil-based agents, the current situation is to frequently replace the lubricating fluid, which improves processing efficiency, precision, and economy in metal machining. In today's world, there is a strong desire to develop a new lubricant to replace conventional lubricants. In view of this current situation, we conducted research to obtain a new oily agent that has a better oily effect than the above-mentioned fatty acids and eliminates the above-mentioned drawbacks of the same fatty acids. or containing a cationic nitrogen atom with a molecular weight of 500 or more
A water-soluble cationic condensate with a molecular weight of less than 1,000 is useful as an oily agent, and by using the condensate alone or in combination with animal and vegetable oils, mineral oils, extreme pressure additives, etc., it can be used to replace conventional lubricants. It has been discovered that the various performances of this material can be greatly improved, and as a result, it is possible to improve efficiency, precision, and economy in metal processing. That is, the present invention has an average molecular weight obtained by reacting an aliphatic dicarboxylic acid having 6 to 16 carbon atoms with a polyamine having the following general formulas (a) to (e).
It is characterized by containing a water-soluble cationic compound obtained by neutralizing a condensate of 500 or more and less than 1000 with one or more of the phosphorus oxygen acids shown in (1) to (3) below. This is a composition for metal processing. (a) General formula Compound represented by the formula In the formula, R ₁ to _{R 4} are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. R ₅ is an alkylene group having 1 to 4 carbon atoms. (b) General formula A compound represented by the formula, where R ₁ to R ₄ and R ₇ are H or have 1 carbon atom
-3 alkyl groups, at least one of which is H. R ₅ and R ₆ have 1 or more carbon atoms
4 is an alkylene group. (c) A compound represented by the general formula H ₂ N (-C ₂ H ₄ NH〓 _o H n in the formula is an integer of 3 to 5. (d) General formula H ₂ N (-CH ₂ -) _o Compound represented by NH ₂ In the formula, n is an integer of 2 to 4. (e) Basic nitrogen compound having a hydroxyl group shown below Ethylaminoethanolamine, N-2-oxypropylamine, 1,2-bis (hydroxyethylamino)ethane, 1,3-diamino-2-propanol, 2-hydroxyethylaminopropylamine, N,N'-bis(hydroxyethyl)
Diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2-oxypropyl-triethylenetetramine (1) Phosphoric acid, phosphorous acid, hypophosphorous acid, perphosphoric acid (2) Pyrophosphoric acid, trimetaphosphoric acid, tetramethalin A condensate of a phosphorus oxyacid selected from acids, pyrophosphorous acid, polymethphosphorous acid, and disuperphosphoric acid (3) Compounds represented by the following formulas () to () Next, a specific configuration of the present invention will be explained. The present invention provides a metal processing composition containing a water-soluble cationic compound having a basic nitrogen atom or a cationic nitrogen atom whose counter anion is an oxygen acid of phosphorus, and having an average molecular weight of 500 or more and less than 1000. It is something that provides something. The water-soluble cationic compound may be used alone or in combination with animal and vegetable oils, mineral oils, fatty acid esters, extreme pressure additives,
It is used in combination with emulsifiers and other substances that are conventional lubricating oil components except for anionic compounds and fatty acids. The water-soluble cationic compound can be easily obtained by neutralizing the condensation product of aliphatic dicarboxylic acids and amines with phosphorus oxygen acids. The aliphatic dicarboxylic acid has 2 to 20 carbon atoms.
Linear and branched saturated or unsaturated dicarboxylic acids and dimer acids can be used, but when the condensation product of these dicarboxylic acids and basic nitrogen compounds is converted to a water-soluble cationic compound using a counter anion, If the number of carbon atoms exceeds 16, sufficient water solubility cannot be imparted, and therefore, in order to provide the desired water solubility, the number of carbon atoms is preferably 16 or less. On the other hand, if the number of carbon atoms is less than 6, the expected lubricity cannot be imparted. Therefore, in order to provide the desired lubricity, it is preferable that the number of carbon atoms is 6 or more. The amines may be compounds that contain two or more basic nitrogen atoms and can undergo a condensation reaction with an aliphatic dicarboxylic acid, but if they have an alkyl substituent, the number of carbon atoms in the alkyl group must be 3 or less. Regarding the alkylene group, a compound having 4 or less carbon atoms is preferable for obtaining a water-soluble cationic compound. Furthermore, ethylaminoethanolamine, N-2
-oxypropylamine, 1,2-bis(hydroxyethylamino)ethane, 1,3-diamino-
Examples include basic nitrogen compounds having a hydroxyl group, such as 2-propanol, 2-hydroxyethylaminopropylamine, 2-hydroxypropyl-trimethylenetetramine, and 2-N oxypropyl-triethylenetetramine. In the above-mentioned condensation reaction of aliphatic dicarboxylic acid and amines, the molar ratio of both is 1:2 to 2:1, respectively.
However, a range of 1:1 to 1:1.5 is preferred in order for the product to exhibit useful lubricity and water solubility. Next, the counter anions that impart water-soluble cationic properties to the condensate include organic acid ions such as acetate ion, oxalate ion, and citrate ion, as well as oxyacid ions such as chloride ion, nitrate ion, sulfate ion, and phosphorus. , boric acid ions and other inorganic acid ions, but phosphorus oxygen acid ions are preferred in order to provide useful lubricity and rust prevention, and the amount thereof is greater than the basic nitrogen excluding the amidic nitrogen atoms in the condensate. 20~ of atoms
100 mol%, preferably 50 to 100 mol%. The molecular weight of the water-soluble cationic compound has an appropriate range in terms of water solubility, lubricity and secondary performance when used in metal processing. In other words, in order to easily impart water solubility industrially, it is preferable that the average molecular weight is less than 1000; if it exceeds this, it will be extremely difficult to impart water solubility, and even if it is possible to do so, it will be difficult to impart water solubility. When dried, the water-soluble cationic compound forms a film on processed products, processing machines, etc., resulting in a decrease in the appearance of the product and the accuracy of machine operation. Regarding lubricity, no significant results are observed when the average molecular weight is less than 500, and the expected performance is obtained when the average molecular weight is 500 or more. Therefore, the water-soluble cationic compound preferably has an average molecular weight in the range of 500 or more and less than 1000. The water-soluble cationic compound was prepared by placing a predetermined amount of the aliphatic dicarboxylic acid and amines into an iron reactor equipped with a thermometer, nitrogen gas inlet tube, stirrer, and backflow cooling tube via a dehydration tube, and placing it in a nitrogen atmosphere. , 160～
A dehydration reaction is carried out under refluxing of xylene at 170°C for 4 to 5 hours, and this is added to water containing a predetermined amount of counter anions determined from the total amine side of the product, and dissolved by heating appropriately with stirring. easily obtained by In order to use the water-soluble cationic compound thus obtained as a lubricant for metal processing, it can be used in the form of a single aqueous solution, or in the form of a base oil or a conventional lubricant.
Among the components collectively called oily agents, extreme pressure additives, emulsifiers, antirust additives, preservatives, etc., it is mixed with all substances other than anionic compounds and fatty acids in any proportion. The metal processing composition containing the water-soluble cationic compound in the above form has excellent lubricity, and furthermore, the composition containing the conventional fatty acid type oily agent exhibits an abnormal reduction in the concentration of fatty acids in the liquid due to metal soap formation. It has characteristics such as no fluctuation in lubricity or acceleration of oil deterioration. Next, examples will be shown in which the metal processing composition of the present invention is applied to cutting, grinding, rolling, and drawing. Table 1 is attached to help understand the preferred embodiments of each component described in the text. The carbon number range of aliphatic dicarboxylic acids is shown in Nos. 1, 2, 3, 20, and 21 in the table. The carbon number range of the alkyl group of amines is shown in No. 4, 27, 29, and 32 in the table, and the carbon number range of the same alkylene group is shown in No. 30 and 31 in the table. Examples of basic nitrogen compounds with hydroxyl groups are shown in the table.
Shown in No.27. The molecular weight ranges of the water-soluble cationic compounds are shown in Nos. 2, 11, 22, and 24 in the table.

【table】

〔Composition〕

・ Phosphoric acid neutralized product of condensation reaction product (average molecular weight 790) of 2 moles of 1,10 dicarboxydecane and 3 moles of triethylenetetramine (using 50 mole% phosphoric acid based on basic nitrogen)... 20 parts/Pentaerythritol sesquioleate
...5 parts, ester of polyethylene glycol and tallow fatty acid with an average molecular weight of 400 ...3 parts, machine oil 30 parts, water 40 parts diluted 40 times with tap water and used as a lubricant for cutting cast iron brake drums. Applied. The frequency of tool replacement due to tool wear is reduced by 20% compared to conventional lubricants, and the liquid separation over time that was previously observed is eliminated. Example 3 Phosphoric acid neutralized product of condensation reaction product (average molecular weight 790) of 2 mol of 1,10 dicarboxydecane and 3 mol of triethylenetetramine (average molecular weight 790)
A 1.0% aqueous solution of phosphoric acid (using mol% phosphoric acid) was applied as a lubricant for grinding a steel crankshaft. The number of workpieces that can be processed before the grindstone is re-ground is five times greater than with conventional lubricants. In addition, the by-product grinding powder flows well in the liquid and does not accumulate, making it easy to recover and clean the liquid, and reducing the amount of dirt around the grindstone and machine. Example 4 A phosphoric acid neutralized product (average molecular weight 740) of a condensation reaction product of adipic acid, 1 mol, 1,10 dicarboxydecane, 1 mol, and triethylenetetramine 3 mol (average molecular weight 740) (75 mol % based on basic nitrogen) using phosphoric acid)
A 2.5% aqueous solution was applied as a lubricant for grinding steel materials. When the contact arc length between the grinding wheel and the workpiece is 25 mm, the grinding resistance is reduced by 21% compared to conventional lubricants. Example 5 Pyrophosphoric acid neutralization product of condensation reaction product (average molecular weight 790) of 2 mol of 1,10 dicarboxydecane and 3 mol of triethylenetetramine (using 75 mol% pyrophosphoric acid based on basic nitrogen) A 0.1% aqueous solution of was applied as a lubricant for cold rolling of steel sheets. The rolling load at a reduction rate of 50% was reduced by 10% compared to conventional lubricating oil. Example 6 A phosphoric acid neutralized product (average molecular weight 740) of a condensation reaction product (average molecular weight 740) of 2 mol of 1,10 dicarboxydecane, 1.5 mol of diethylenetriamine, and 1.5 mol of triethylenetetramine (75 mol% based on basic nitrogen) (A) in Table 2 consisting of (using phosphoric acid), machine oil and water
The composition of ~(c) was applied as a lubricant for cold rolling of steel materials. The rolling load at a rolling reduction of 50% is reduced by more than 10% compared to conventional lubricants, and there is very little dirt on the rolls and products, and even if the rolled plate is annealed under normal conditions, A clean product with no carbon stains was obtained.

【table】

Claims (1)

[Scope of Claims] 1. A condensation product having an average molecular weight of 500 or more and less than 1000 obtained by reacting an aliphatic dicarboxylic acid having 6 to 16 carbon atoms with a polyamine having the general formulas (a) to (e) below. A composition for metal processing, characterized in that it contains a water-soluble cationic compound obtained by neutralizing the body with one or more of the phosphorus oxyacids shown in (1) to (3) below. . (a) General formula Compound represented by the formula In the formula, R ₁ to _{R 4} are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. R ₆ is an alkylene group having 1 to 4 carbon atoms. (b) General formula A compound represented by the formula, where R ₁ to R ₄ and R ₇ are H or have 1 carbon atom
-3 alkyl groups, at least one of which is H. R ₅ and R ₆ have 1 or more carbon atoms
4 is an alkylene group. (c) A compound represented by the general formula H ₂ N (-C ₂ H ₄ NH- _o H n in the formula is an integer of 3 to 5. (d) General formula H ₂ N (-CH ₂ )- _o Compound represented by NH ₂ In the formula, n is an integer of 2 to 4. (e) Basic nitrogen compound having a hydroxyl group shown below Ethylaminoethanolamine, N-2-oxypropylamine, 1,2-bis (hydroxyethylamino)ethane, 1,3-diamino-2-propanol, 2-hydroxyethylaminopropylamine, N,N'-bis(hydroxyethyl)
Diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2-oxypropyl-triethylenetetramine (1) Phosphoric acid, phosphorous acid, hypophosphorous acid, perphosphoric acid (2) Pyrophosphoric acid, trimetaphosphoric acid, tetramethalin A condensate of a phosphorus oxyacid selected from acids, pyrophosphorous acid, polymethphosphorous acid, and disuperphosphoric acid (3) Compounds represented by the following formulas () to ()