JPS60235897A - Metal working composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent lubricity and does not cause abnormal lowering in a fatty acid concn. in a soln. due to the formation of metallic soap. containing a specified water-soluble cationic compd. CONSTITUTION:A mixture consisting of a 6-16C aliph. dicarboxylic acid and a 17-22C aliph. dicarboxylic acid is reacted with at least one compd. contg. at least two basic N atoms selected from among compds. of formulas I -III (wherein R1-R4, R7 are each H, a 1-4C alkyl and at least one thereof is H; R5, R6 are each a 1-4C alkylene; n is 3-5), ethylaminoethanol, 1,2-bis(hydroxy ethylamino) ethane, etc. in a molar ratio of 1:2-2:1 to obtain a condensate having an average MW of 500-100. The condensate is neutralized with at least one oxyacid of P selected from among phosphoric acid, phosphorous acid, condensates of oxyacid of P (e.g. pyrophosphoric acid) and compds. of formulas IV-VI to obtain a water-soluble cationic compd., which is then dissolved in water or a base oil.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to compositions for metal working. More specifically, the present invention relates to a metal working composition containing a water-soluble cationized metal material whose counter-anion is a phosphorous oxygen acid.

BACKGROUND ART Conventionally, lubricants used in metal machining, such as rolling, drawing, cutting, and grinding, use animal and vegetable oils, mineral oils, etc. as a base oil, and fatty acids, alcohols, etc. as oily agents. The composition contains organic phosphorus compounds, organic chlorine compounds, etc. as extreme pressure additives, and an emulsifier as necessary. That lubrication book.

Designed to be effective. Among the basic threads mentioned above, the one that greatly influences the lubricating performance is the oil-based agent. Conventionally, fatty acids having about 8 to 20 carbon atoms, their dimer acids, and their salts have been used as oil-based agents. There is. During metal processing, fatty acids react with each metal on the surface of tools and workpieces, and are strongly adsorbed to the metal surface.
It has been widely used in the past to exhibit good lubrication properties, but on the other hand, it naturally reacts to abrasive metal powder generated during machining, and then produces metal soap and removes it from the lubricating fluid. It easily disappears and discards. As a result, there is a problem in that the lubrication performance changes over time, which impedes work stability. In addition, the produced metal soap impedes the stability of the lubricating fluid, often rendering the fluid unusable. Furthermore, since it partially deteriorates due to the heat and shearing force generated during metal processing, it accelerates the deterioration of the floating oil content, significantly contaminating processed products and processing machines, and requiring a large amount of expense to clean them. In order to avoid these problems caused by the use of fatty acid-based oil-based agents, the lubricating fluid is currently being replaced frequently.
Nowadays, where precision and economy are in high demand, the development of a new lubricant has been strongly desired.

Purpose of the Invention In view of the current situation, it is an object of the present invention to develop a novel oily agent that has a superior oily effect than the aforementioned fatty acids and eliminates the aforementioned disadvantages of the same fatty acids.

Structure of the Invention The present invention provides an aliphatic dicarzene acid having 6 to 16 carbon atoms (
A dicarzene acid mixture consisting of aliphatic dicarginic acid (A2) having 17 to 22 carbon atoms and a molar ratio of (AI):(A2) of 1:3 to 3:1; )
The following (1
This is a metal processing composition characterized by containing a water-soluble cationic compound obtained by neutralizing with one or more of the phosphorus oxygen acids shown in 1 to 3).

8.1 to B4 in the formula are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H.

R5 is an alkylene group having 1 to 4 carbon atoms.

The compound shown in

In the formula, R, -R, and B17 are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is
One is H.

R,6 and B,6 are alkylene groups having 1 to 4 carbon atoms.

(c) General formula H! A compound represented by N→02 H4N H.

n in the formula is an integer of 3 to 5.

(d) A basic nitrogen compound having a hydroxyl group shown below.

Ethylamineethanolamine, 1,2-bis(hydroxyethylamine)ethane, 1゜3-diamino-2-pronognol, 2-hydroxyethylaminoprobylamine, N,N'-bis(hydroxyethyl)diethylenetriamine, 2- Hydroxypropyl-trimethylenetetramine, N-2-oxypropyl-triethylenetetramine [+1 Phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid (2) Birophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, pyrophosphorous acid A condensate of phosphorous oxyacids selected from acids, polymetathosphous acids, disuperphosphoric acids.

(3) Compounds represented by the following formulas (1) to ++*0.

” H 00HO The above active ingredients or raw materials of the present invention will be explained in detail below.

(Water-soluble cationic compound) The water-soluble cationic compound which is a portion of the composite bottom of the present invention is a condensation product of aliphatic dicarzene acids and amines = i,
It can be easily obtained by neutralizing IJ with oxygen acids.

For water-soluble cationic compounds, use a thermometer, nitrogen gas introduction tube,
A predetermined amount of the aliphatic dicarginic acid and amines were placed in an iron reaction tube equipped with a stirrer and a counterflow cooling tube via a dehydration tube, and the mixture was heated at 160 to 170°C for 4 to 5 hours in a nitrogen atmosphere.
A dehydration reaction is performed under refluxing of Quijirole to create a condensate,
This can be easily obtained by adding it to water containing a predetermined amount of counter anions based on the total amine value of the raw bottom material, and heating and dissolving it while stirring.

The average molecular weight of the condensate has an appropriate range for imparting solubility to the water-soluble cationic compound and lubricity and secondary performance when used in metal processing.

That is, in order to easily impart water solubility industrially, it is preferable that the average molecular weight of the condensate is less than 1000, and if it exceeds that, it is extremely difficult to impart water solubility.
Even if this were possible, the water-soluble cationic compound would form a film on processed products, processing machines, etc. when dried, resulting in a decrease in the appearance of the product and the accuracy of machine operation. Regarding lubricity, no significant results were observed when the average molecular weight was less than 500,
Expected performance can be obtained at 500 or higher. Therefore,
The average molecular f of the condensate is preferably in the range of 500 or more and less than 1000.

The water-soluble cationic compound thus obtained is used as a lubricant for metal processing, either in the form of a single aqueous solution, or in conventional lubricating oils such as base oil, oily agent, extreme pressure additive, emulsifier, Among the components collectively called rust preventive additives, preservatives, etc., all substances other than anionic compounds and fatty acids may be mixed in any proportion.

(Aliphatic dicarboxylic acid) As the aliphatic dicarboxylic acid used to produce the water-soluble cationic compound, linear dicarboxylic acids or branched dicarboxylic acids can be used. These dicarboxylic acids may be saturated or unsaturated acids.

In the present invention, a dicarboxylic acid having 6 to 16 carbon atoms (A1) and a dicarboxylic acid having 17 to 22 carbon atoms (A2
) is essential.

When the condensation product of an aliphatic dicarboxylic acid and a basic nitrogen compound is neutralized using a counter anion to convert it into a water-soluble cationic compound, the expected result is that dicarginic acid is only (A1). Lubricity cannot be imparted, and (A2) alone cannot impart sufficient water solubility. (A1) and (A2
) is 3:1 to 1:3 (molar ratio).

If the ratio of (A+) is larger than this, the lubricity will decrease,
If the ratio of (A2) is larger than this, the water solubility will be insufficient.

(Amines) As amines for producing water-soluble cationic compounds, compounds containing two or more basic nitrogen atoms,
Any compound that can undergo a condensation reaction with an aliphatic dicarboxylic acid may be used, but if it has an alkyl substituent, the alkyl group has 3 or less carbon atoms, and if the alkylene group has 4 or less carbon atoms, it is water-soluble. Preferred for obtaining compounds.

Further examples of amines include ethylaminoethanolamine, l,2-bis(hydroxyethylamino)ethane, 1,3-diamino-2-propanol, 2-hydroxyethylaminoprobylamine, N,N'-bis( Examples include basic nitrogen compounds having a hydroxyl group, such as hydroxyethyl)diethylenetriamine and N-2-oxypropyl-triethylenetetramine.

(Condensation reaction) In the condensation reaction between the aliphatic dicarboxylic acid and amines, the molar ratio between the two may be in the range of 1:2 to 2:1, but the product may have useful lubricity and water solubility. A range of 1:1 to 1:1.5 is preferred.

(Counter anion) Next, counter anions for neutralizing the condensate to obtain a water-soluble cationic compound include organic acid ions such as acetate ions, oxalate ions, and citrate ions, and also sodium ions. , nitrate ion, sulfate ion, phosphorus oxygen acid ion,
Examples include inorganic acid ions such as boric acid ions, but phosphorus oxygen acid ions are preferred to provide useful lubricity and rust prevention, and other counter anions are preferred for providing useful lubricity and rust prevention. It is unsuitable due to its shortcomings. The amount of phosphorus oxygen acid is between 2 and 1 equivalent, preferably between 0.5 and 1 equivalent.

Examples In order to make it easier to understand the present invention, Examples 1 to 6f are given below.
However, the following examples are not intended to limit the invention. In addition, reference examples in which the metal processing composition of the present invention is applied to cutting, grinding, rolling, and drawing are also shown below.

In addition, in the following, "part" means "part by weight", and "%" means "part by weight".
” means “% by weight”.

Example 1 A phosphoric acid neutralized product (0,
A 2.5% aqueous solution of 75% phosphoric acid was applied as a lubricant for cutting a cast iron brake drum.

Tool replacement frequency due to tool wear is 3 times lower than with conventional lubricants.
5 times less, and there are no problems such as liquid separation or spoilage over time that were conventionally seen, and the life of the liquid can be extended.

Example 2 Sebacic acid, 1 mol, phosphoric acid neutralized product (0.5 equivalents) of the condensation reaction product (average molecular weight: 910) of 1 mol of 1.18-octadecanedicalinic acid and 3 mol of triethylenetetramine 20 parts - Bentaerythritol sesquioleate 5 parts - Ester of polyethylene glycol with an average molecular weight of 400 and beef tallow fatty acid - 3 parts - Machine oil 30 parts - 40 parts of water was diluted 40 times with tap water and applied as a lubricant for cutting a cast iron brake drum.

Tool replacement frequency due to tool wear is 3 times lower than with conventional lubricants.
0% reduction, -! The liquid separation over time that was previously seen is no longer present.

Example 3 Neutralization with phosphoric acid of a condensation reaction product (average molecular weight 930) of 1 mol of adipic acid, 1 mol of 1.16-hexazocandical dinic acid, 1.5 mol of diethylenetriamine, and 1.5 mol of triethylenetetramine A 1.0% aqueous solution of phosphoric acid (using 0.75 equivalents of phosphoric acid) was applied as a lubricant for grinding a steel crankshaft.

The number of workpieces that can be machined before re-sharpening the whetstone is seven times that of conventional lubricants. ′! In addition, the by-produced grinding powder flows well in the liquid and does not accumulate, making it easy to recover and clean the liquid, and there is less dirt around the grindstone and the machine.

Example 4 A phosphoric acid neutralized product (average molecular weight 675) of a condensation reaction product (average molecular weight 675) of 1 mol of adipic acid, 1 mol of 1.16-hexazocandicardonic acid, 1.5 mol of tetramethylenediamine, and 1.5 mol of diethylenetriamine (using an equivalent amount of phosphoric acid), 2.
A 5CH aqueous solution was applied as a lubricant for grinding steel materials.

The grinding resistance when the contact arc length between the grindstone and the workpiece was 25 m was reduced by 25% compared to conventional lubricants.

Example 5.1 Condensation reaction product of 1 mol of sebacic acid, 1 mol of 1.18-octadecanedicarzenic acid and 3 mol of triethylenetetramine (average molecular weight: 1910) neutralized with phosphoric acid (using equivalent amount of phosphoric acid) A 0.1% aqueous solution was applied as a lubricating fluid for cold rolling of steel sheets.

The rolling load at a rolling reduction of 50% was reduced by 15 cm compared to conventional lubricating oil.

Example 6 Birophosphoric acid neutralized product (0
, 75 of the present invention), machine oil and water were applied as a lubricating fluid for cold rolling of steel materials.

The rolling load at a rolling reduction of 50% is reduced by more than 15 inches compared to conventional lubricating oils, and there is very little staining on rolls and products, and even if the rolled plate is annealed under normal conditions, A clean product with no cardan stains was obtained.

Table 1 Next, Table 2 shows Examples 1 to 6, other examples, and reference examples.

Effects of the Invention The composition Fi for metal processing of the present invention has excellent lubricity and, moreover, the composition containing a conventional fatty acid type oily agent exhibits an abnormal reduction in the concentration of fatty acids in the liquid due to metal soap insect repellent - Fluctuation in lubricity, oil content It has the characteristic of accelerating deterioration, etc.

Applicant Nippon Steel Tube Co., Ltd. and one other person Agent Patent attorney Minoru Isaka Continuation of the procedure amendment on page 1 May 18, 1980 Commissioner of the Patent Office Attachment To Wainu 1, Indication of case Enter f7 → / ,,; P 9 Showa 59
Patent application 2 filed on May 9, 2013. Name of invention: Composition for metal processing 3. Relationship with the amended person's case. Name of patent applicant: Nippon Netkan Co., Ltd. (and one other person). 4. Address of agent: Port of Tokyo. Ono Building, 1-21-11 Nishi-Shinbashi, Ward Voluntary amendment 6 Number of inventions increased by the amendment 0 7, Column 8 for detailed explanation of the invention in the specification to be amended Contents of the amendment

Claims (1)

[Claims] Aliphatic dicarmenic acid having 6 to 16 carbon atoms (A1) and aliphatic dicarzenic acid having 17 to 22 carbon atoms (A2)
Tokaranashi, the molar ratio of (A+): (A2) is 1:3
The average molecular weight obtained by reacting a dicarzenic acid mixture having a ratio of ~3:1 with one or more of the compounds containing two or more basic nitrogen atoms represented by fa) to d) below is 500 or more. A metal characterized by containing a water-soluble cationic compound obtained by neutralizing a condensate of less than 1000 with one or more of the phosphorus oxygen acids shown in (1) to 3) below. Composition for processing. In the formula, R, 1-R, is H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. B5 is an alkylene group having 1 to 4 carbon atoms. A compound represented by 7. In the formula, R, 1-R, 4 and B7 are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. R5 and R16 are alkylene compounds having 1 to 4 carbon atoms. n in the formula is an integer of 3 to 5. (d) A basic nitrogen compound having a hydroxyl group shown below. Ethylamineethanolamine, 1,2-bis(hydroxyethylamine)ethane, 1゜3-diamino-2-zolononol, 2-hydroxyethelaminopropylamine, N,N'-bis(hydroxyethyl)diethylenetriane, 2 -Hydroxypropyl-trimethylenetetramine, N-2-oxypropyl-triethylenetetramine (1) Phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid (2) Pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, pyro A condensate of a phosphorous oxyacid selected from phosphorous acid, polymetaphosphorous acid, and disuperphosphoric acid. (3) A compound represented by the following formula (1) to (2). (1)N (-0H2-P-OH)s OH OO 111