JPS61296094A - Metal processing composition - Google Patents

Abstract

PURPOSE:A novel metal processing composition having improved oily effect, processing efficiency, precision and economic efficiency, containing a water dispersible cationic compound obtained by neutralizing a specific condensate with a specified phosphorus oxyacid and a specific fatty acid. CONSTITUTION:The aimed composition containing a water dispersible cationic compound obtained by neutralizing (A) a condensate prepared by reacting (i) an aliphatic basic carboxylic acid such as adipic acid, azelaic acid, etc. with (ii) a basic nitrogen compound shown by the formula I-formula III (R1-R5 are H or 1-3C alkyl; m and n are 2-6; p is 3-5), etc., with (B) a phosphorus oxyacid such as phosphoric acid (phosphorous acid), pyrophosphoric acid, compound shown by the formula VI, etc., and 6-22C fatty acid into 6-9pH.

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 water-soluble cationic compound obtained by neutralizing a condensate obtained by reacting an aliphatic poly-1'11-carboxylic acid with a basic nitrogen compound with a phosphorus oxygen acid and a fatty acid. The present invention relates to a metal processing composition containing an ionic compound.

Conventional technology Conventionally, lubricants used for metal machining, such as drawing, cutting, and φ grinding, use animal and vegetable fats, mineral oils, etc. as a base oil, to which fatty acids, alcohols, etc. are added as oily agents. This composition contains organic phosphorus compounds, organic chlorine compounds, etc. as pressure additives, and an emulsifier as necessary. It is designed to exhibit its lubricating effect. -1. Among the basic compositions listed above, the one that greatly influences the lubricating performance is the oily agent, which has traditionally been made of fatty acids having about 8 to 20 carbon atoms, their dimer acids, and their salts. It is used. When processing metals, fatty acids have traditionally been widely used because they react with the respective metals on the surfaces of tools and workpieces, are strongly adsorbed and arranged on the metal surfaces, and exhibit good lubricity. However, on the other hand, as a matter of course, fatty acids react with wear metal powder generated during processing to produce metal soap, so they easily disappear from the lubricating fluid. As a result, fatty acids cause a problem in that the lubricating performance changes over time and hinders work stability. In addition, the generated metal soap impedes the stability of the lubricating liquid, often rendering the lubricating liquid unusable.

Furthermore, fatty acids are partially degraded by the heat and shearing forces generated during metal processing, which accelerates the deterioration of floating oil components, resulting in significant contamination of processed products and processing machinery, requiring much effort to clean them. costs. In order to avoid the various problems that arise from the use of fatty acid-based oil-based agents, the current situation is that lubricating fluids are frequently replaced.
Currently, there is a strong demand for processing efficiency, precision, and economy in metal machining, and the development of new lubricants is strongly desired.

Problems to be Solved by the Invention In view of the current situation, an object of the present invention is to provide a novel oil-based agent that has a superior oil-based effect than the above-mentioned fatty acids and eliminates the above-mentioned disadvantages of the same fatty acids. .

Means for Solving the Problems The present invention provides an aliphatic polybasic carboxylic acid and one or more basic nitrogen compounds I- shown in (a) to (e) shown below. (I) The condensate is shown below (A)
Contains an ice-dispersible cationic compound obtained by neutralizing one or more of the phosphorus oxygen acids shown in (c) to (c) with a fatty acid having 6 to 22 carbon atoms. This is a characteristic composition for metal adding L.

(a) A compound represented by the general formula % (wherein R, to R4 are H or an alkyl group having 1 to 3 carbon atoms, at least one of which is H, and n is 2 ), (b) a compound represented by the general formula % (wherein R1 to R5 are H or an argyl group having 1 to 3 carbon atoms, and at least one of them is is H, m and n are integers from 2 to 6, and both may be the same or different.), (C) a compound represented by the general formula H2N-(C2H4NH)p-H (however, in the formula p is an integer from 3 to 5.

), (d) ethylaminoethanolamine, 1,2-bis(
hydroxyethylamino)ethane, 1゜3-diamino-
selected from the group consisting of 2-propatur, 2-hydroxyethylaminoprobylamine, N,N'-bis(hydroxyethyl)diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2-year-old pheasantpropyl-triethylenetetramine (e) Polyethyleneimine having an average molecular weight of 500 or more and c'100,000 or less, (a) Phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, (B) ) a condensate of a phosphorus oxyacid selected from birophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, pyrophosphorous acid, polymethphosphorous acid, and diperphosphoric acid; A compound represented by
(i) 0 N (-CH2-P-OH) 3 H 0HCH30H (iii) 0 ■ (HO-P-CH2) 2 =N -(CH2)
2-H Mi-N= (CH2-P-0)1)2 臇OH The above-mentioned present invention will be explained in detail below.

(Aliphatic polybasic carboxylic acid) The aliphatic polybasic carboxylic acid used in the present invention is a saturated or unsaturated dicarboxylic acid with a linear or branched structure having 6 to 54 carbon atoms. and polymerized fatty acids such as dimer acid or trimer acid.

These aliphatic polybasic carboxylic acids may be used alone or in combination of two or more.

If the aliphatic polybasic carboxylic acid has less than 6 carbon atoms, significant lubricity cannot be imparted. Also, the number of carbon atoms is 54
Since aliphatic polybasic carboxylic acids exceeding 50% are not produced on an industrial scale, they are excluded from the scope of the present invention.

Examples of aliphatic polybasic carboxylic acids that can be used in the present invention are as follows.

Adipic acid, azelaic acid, sebacic acid, l.

lO-decanedicarboxylic acid, 1.14-tetradecanedicarboxylic acid, 1.18-octadecanedicarboxylic acid, HOOCCI((CH2) 5COOH cloud C4H92-butyloctanedioic acid HOOC(CH2)5 CH(CH2)to-2R5 -COOI( 7-Nityloctadecanedioic acid HOOC (C
H2)s -CH=CH-(CH2)b C00H 8-hexadecenedioic acid HOOC(CH2)6 -C=CH(CH2)? -H
3 -CH=C-(OH7)6 C0OHCH3 8,13 dimethyl-8,12 monoeicosadienioic acid S, etc. Typical examples of polymerized fatty acids include fatty acids from higher aliphatic monoenoic acids or dienoic acids such as oleic acid or linoleic acid. Examples include mixed acids whose main components are derived dimer acids or trimer acids. Specifically, the above industrially produced acid having 36 to 54 carbon atoms and sold under the name of dimer acid or trimer acid can be used.

(Alkylene diamine) Specific examples of the compound (alkylene diamine) of general formula (a) to be condensed with an aliphatic polybasic carboxylic acid to produce the active ingredient of the composition of the present invention include ethylene diamine, γ-(methyl amino) propylamine, diaminopropane, tetramethylenediamine, N-methyl-propanediamine, N,N'-dimethyl-propanediamine,
N-ethyl-propanediamine, N,N'-diethyl-
Examples include propanediamine.

In these alkylene diamines, R1 to R5
If the number of carbon atoms exceeds 3, it is not preferable because the water dispersibility of the composition of the present invention decreases.

Also, the number of alkylene groups in the alkylene diamine is 1
It is difficult to obtain industrially those having more than 6 alkylene groups, and the use of those having more than 6 alkylene groups is not preferred because the water dispersibility of the composition of the present invention decreases.

(Dialkylenetriamine) Specific examples of the compound (dialkylenetriamine) of general formula (b) to be condensed with an aliphatic polybasic carboxylic acid to produce the active ingredient of the composition of the present invention include diethylenetriamine, methyliminotriamine, Bispropylamine, 1,3
．． 6-) Liaminomethylhexane, N-aminoethyl-
Examples include N-methyl-1,3-diaminopropane and iminobispropylamine.

The reason for limiting the number of carbon atoms in the alkyl group in the dialkylene triamine and the reason for limiting the number of alkylene groups are exactly the same as in the case of alkylene diamine.

(Polyethylene polyamine) In the compound represented by the general formula (C), that is, polyethylene polyamine, which is condensed with a polybasic carboxylic acid in order to produce the active ingredient of the composition of the present invention, the general formula (C
) is 1, it is the same as general formula (a), and n
If is 2, it is the same as the general formula (b), so n is set to be 3 or more. Moreover, those with n of 6 or more are difficult to obtain industrially.

(Polyethyleneimine) The compound (e), polyethyleneimine, to be condensed with a polybasic carboxylic acid to produce the active ingredient of the composition of the present invention has a molecular weight of 500 or more and too or ooo or less. When the molecular m: is less than 500, it becomes difficult to impart water solubility; on the other hand, when the molecular weight is 100,
If it exceeds 000, the product exhibits a high viscosity and becomes extremely difficult to handle.

(Condensate) In the present invention, the average molecular weight of the condensate of the aliphatic polybasic carboxylic acid and the compounds (a) to (e) has an appropriate range.

That is, in order to impart to the condensate the property of industrially easily dispersing it in water, it is preferable that the average molecular weight of the condensate, as measured by the vapor pressure method, be 500 or more and less than 1,000. When the average molecular weight is 1.000 or more -1-, it is extremely difficult to impart water-dispersibility to the cationic compound, and even if it is possible, the water-dispersible cationic compound is When dried, it forms a film on pressure products, processing machines, etc., resulting in poor product appearance and reduced machine operating accuracy. Further, if the average molecular weight is 500 or more, the expected lubricating performance can be obtained, but on the other hand, if the average molecular weight is less than 500, it becomes difficult to impart water dispersibility.

Moreover, aliphatic polybasic carboxylic acid and (a) to (e)
The molar ratio with the basic nitrogen compound ranges from 1:1 to 1:1.
A range of up to 5 is preferred. This is because condensation within this range will yield products that exhibit useful lubricity and water dispersibility.

(Water-dispersible cationic compound) The water-dispersible cationic compound, which is an active ingredient of the composition of the present invention, includes aliphatic polybasic carboxylic acids and amines [i.e., within the scope of the claims of this specification]. (a) or (
It can be easily obtained by adding phosphorus oxygen acids and fatty acids to the condensation product with basic nitrogen compounds belonging to group e) and neutralizing it.

Examples of fatty acids that can be used for this purpose include saturated acids such as hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, tocosanoic acid, decenoic acid, tetradecenoic acid, Mention may be made of unsaturated acids such as octadecenoic acid.

The water-dispersible cationic compound was prepared by adding a predetermined amount of an aliphatic polybasic carboxylic acid and a basic nitrogen compound to an iron reactor equipped with a thermometer, a nitrogen gas inlet tube, a stirrer, and a backflow cooling tube via a dehydration tube. Add pheasant roll and heat to 160℃ in nitrogen atmosphere.
A dehydration reaction is carried out under refluxing at 170°C for 4 to 5 hours to prepare a condensate, and to this a predetermined amount of phosphorus oxygen acid and fatty acid determined from the total amine value of the product is added, and the mixture is stirred. It can be easily obtained by heating appropriately. The ratio of fatty acid and phosphorus oxygen acid added to neutralize the condensate is preferably in the range of 20:80 to 80:20. If it is outside this range, the water-dispersible cationic compound produced will not have sufficient lubricating action.

In addition, the total amount of fatty acids and phosphorus oxygen acids is determined by the pH of the neutralized product being 6.
9. If the pH is less than 6, the rust prevention property will be insufficient, and if it exceeds 9, the lubricity will be insufficient, so both are not preferred. Table 1 specifically shows the water-dispersible cationic compounds of the present invention.

Table 1 Water-dispersible cationic compounds (part 1) Table 1 (
Part 2) Table 1 (Part 3) The water-dispersible cationic compounds No. 2 in Table 1 were manufactured as follows.

1.10 Decanedicarboxylic acid and triethylenetetramine were condensed at a molar ratio of 2/3 to obtain a solid condensate having an average molecular weight of 790.

Add 36.9 g of phosphorous acid (85% aqueous solution) and 31.4 g of dodecanoic acid to 1269 g of water, heat to 80-90°C, add 79 g of the above condensate (pulverized material) while stirring, and form a uniform It was made into a dispersion liquid. After cooling this, 30°C
PH was measured. Its pH was 8.2.

Other compounds were also produced according to No. 2.

In order to provide the water-dispersible cationic compound obtained as described above as a lubricant for metal addition, it may be used alone, and in conventional lubricating oils, base oil, oily agent, extreme pressure It may be used in any proportion by mixing with all substances, excluding anionic compounds and fatty acids, among the components collectively called additives, emulsifiers, anti-rust sardine additives, preservatives, etc.

The above compound or mixture can be used as it is or as an aqueous dispersion.

EXAMPLES In order to make it easier to understand the present invention, Examples 1 to 8 are shown below to specifically explain the present invention.

However, these Examples do not limit the present invention in any way. In addition, in the following, "r part" means "heavy metropolitan area", and "r%" means "weight %".

Example 1 Water-dispersible cationic compound No. 1 shown in Table 1 was applied as a lubricant for cutting a cast iron brake drum.

1- The frequency of tool replacement due to tool wear is reduced by 15% compared to conventional lubricating fluids (i.e. cutting oils equivalent to JIS N2241 W1 class No. 1), and liquid separation over time, which was previously observed, is reduced by 15%. There are no problems such as spoilage, and the lifespan of the lubricant can be extended.

Example 2 Compound No. 2 in Table 1 20 parts Pentaerythritol sesquioleate 5 parts Ester of polyethylene glycol with an average molecular weight of 1400 and beef fatty acid 3 parts Machine oil (
book) 30 copies water
40 parts of the mixture was diluted 40 times with tap water and applied as a lubricant for machining of cast iron drums. - "The frequency of tool replacement due to tool wear is reduced by 30% compared to conventional lubricating fluids (i.e., cutting oil equivalent to JiS N2241 W1 class No. 1), and the liquid separation over time that was conventionally observed is reduced by 30%. lost.

(Note 0) The machine oil used in this example is JIS N223
8 and ISOVG46.

Example 3 A 1.0% aqueous dispersion of compound N083 in Table 1 was applied as a lubricant for grinding a steel crankshaft.

The number of workpieces that can be cut by regrinding of the grindstone is eight times that of conventional lubricants (i.e., cutting oil equivalent to JIS K2241 W2 class No. 1). In addition, the by-product polishing powder flows well in the liquid and does not accumulate, making it easy to recover and clean the liquid, and there was less dirt on the grindstone and less dirt around the machine.

Example 4 Water-dispersible cationic compound (No. in Table 1).

The 2.5% aqueous dispersion of 4) was applied as a lubricant for grinding steel materials. The grinding resistance when the contact arc length between the grinding wheel and the workpiece is 25 mm is that of conventional lubricant (i.e. JIS N
25 compared to cutting oil equivalent to 2241 W2 type No. 1)
% decreased.

Example 5 A 0.1% aqueous dispersion of compound N015 in Table 1 was applied as a lubricant for cold rolling of steel sheets. The rolling load at a downstream ratio of 50% was reduced by 15% compared to conventional lubricating oil (ie, tallow-based cold rolling oil).

Example 6 A 1.0% aqueous dispersion of compound No. 006 in Table 1 was applied as a lubricant for cutting a cast iron brake drum.

Tool replacement frequency due to tool wear is reduced using conventional lubricant (i.e. cutting oil equivalent to JIS N2241 W2 type No. 1).
It has been reduced by 15% compared to the conventional lubricating liquid, and there are no problems such as liquid separation and spoilage over time, which were seen in the past, and the life of the lubricating liquid can be extended.

Example 7 Compositions A, B, and C shown in Table 2 were prepared using compound No. 017 and compounds No. 8 in Table 1, and these were applied as lubricants for cold rolling of steel sheets.

The rolling load at a downstream ratio of 50% is reduced by more than 10% compared to conventional lubricating fluids (i.e. beef tallow-based cold rolling oil), and there is very little staining on the rolls or products, and the rolled plate can be used as is. Even when annealed under these conditions, a clean product with no carbon stains was obtained.

Table 2 Sample composition and rolling load (Part 1) Table 2 (Part 2) Example 8 Powder of the compound No. 9 in Table 1 was heated to 150°C and melted, and a carbide wire drawing die ( It was applied to wire drawing using a hole diameter of 4 mm and a die angle of 7 degrees.

The pulling force before processing was 20% lower than when rapeseed oil was used as the lubricant, and 25% lower than when a mineral oil-based lubricant with 10% chlorine content was used. Chlorine content lO used at this time
% mineral oil-based lubricant has the following composition.

Machine oil (JIS N2238 ISOVG46 equivalent) 60% rapeseed oil
20% highly sensitive chlorinated paraffin (chlorine content 50% by weight) 20% by weight Effects of the Invention The metalworking composition of the present invention has superior lubricity than conventional lubricant compositions consisting of oily components, and is less likely to produce metal soap. There is no abnormal decrease in the concentration of fatty acids in the liquid, no fluctuation in lubricity, and no acceleration of oil content deterioration, resulting in significant progress in processing efficiency, precision, and economy.

Claims (1)

[Scope of Claims] A condensate obtained by reacting an aliphatic polybasic carboxylic acid with one or more basic nitrogen compounds shown in (a) to (e) below, It is characterized by containing a water-dispersible cationic compound obtained by neutralizing one or more of the phosphorus oxygen acids shown in ) to (c) and a fatty acid having 6 to 22 carbon atoms. A composition for metal processing. (a) A compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 to R_4 in the formula are H or an alkyl group having 1 to 3 carbon atoms,
At least one of them is H, and n is an integer from 2 to 6. ), (b) A compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 to R_5 in the formula are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is is H, m and n are integers from 2 to 6, and both may be the same or different.), (c) A compound represented by the general formula H_2N-(C_2H_4NH)p-H (provided that p is an integer from 3 to 5), (d) ethylaminoethanolamine, 1,2-bis(
hydroxyethylamino)ethane, 1,3-diamino-
a hydroxyl group selected from the group consisting of 2-propanol, 2-hydroxyethylaminopropylamine, N,N'-bis(hydroxyethyl)diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2oxypropyl-triethylenetetramine (e) polyethyleneimine with an average molecular weight of 500 or more and 100,000 or less, (a) phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, (b) pyrophosphoric acid, trimethalin acid, a condensate of a phosphorus oxyacid selected from tetrametaphosphoric acid, pyrophosphorous acid, and disuperphosphoric acid, (c) a compound represented by the following formula (i) to (iii), (i) ▲ formula, There are chemical formulas, tables, etc.▼ (ii)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (iii)▲There are mathematical formulas, chemical formulas, tables, etc.▼