JPS5867792A - Aqueous processing agent for metal - Google Patents

Abstract

PURPOSE:An aqueous processing agent for metal, safe to the human body, having improved cutting properties and corrosion resistance, comprising a polyaminoamide compound(salt), obtained by reacting a specific polyamine with a specified vinyl monocarboxylic acid, etc. in a particular ratio under heating. CONSTITUTION:(A) 1mol polyamine having two or more primary or secondary amino groups in the molecule is reacted with (B) 0.1-1.9mol equivalent vinyl monocarboxylic acid(ester) or organic polycarboxylic acid(ester) having two or more carboxylic groups in the molecule under heating, to give a polyaminoamide compound(salt), which is dispersed or diluted in water, to give the desired aqueous processing agent for metal.

Description

[Detailed description of the invention] The present invention is a book related to water-based metal processing agents.

For metal processing, such as cutting, grinding, hardening, and plastic deformation, oil-based or water-based Metalworking agents are widely used.

There are many types of metal processing agents, and those that best suit the working conditions are appropriately selected and used.

Water-based metal processing agents are still small in variety and quantity compared to oil-based ones, but there is an extremely large potential demand for them in view of the recent trend toward resource conservation.

Among water-based metal processing agents, those that mix nitrite and triethanolamine have a better track record than conventional ones.
Although the effect was even better,
In recent years, it has been discovered that these substances produce nitrosamines, which are carcinogens, when used, and the use of these substances is gradually being phased out. Since then, the metal processing agent industry has continued to search for alternatives.

Currently available metal processing agents include the salt of sepathic acid and triethanolamine and the alkali salt of paratertiary butylbenzoic acid, but the salt of sepathic acid and triethanolamine is still insufficient. On the other hand, alkaline salts of tertiary butyl benzoic acid have been questioned from the viewpoint of oral toxicity.

Despite the fact that various water-based metal processing agents are currently used, they have advantages but also disadvantages, and are therefore of practical use only within a limited range depending on the purpose. The current situation is that

In view of the current situation, the present inventors continued their chain research and found that (1), [a) a polyamine having at least two primary or secondary amino groups in the molecule; A polyaminoamide compound or a salt thereof obtained by heating and warping an organic polycarboxylic acid having at least two carboxyl groups, (21(a) a polyamine having at least two primary and secondary amino groups in the molecule, (b) A polyaminoamide compound or a salt thereof obtained by heat-reacting an organic polycarboxylic acid having at least two carboxyl groups in the molecule and an (el monocarboxylic acid), the above substances (1) and (2) in water. Diluted with L*4, it is safe for the human body,
At the same time, it was discovered that it has excellent machinability, grindability, and antirust properties necessary as a metal processing agent, leading to the present invention. 'Excellent machinability means a low friction coefficient, and excellent grindability means a wide range of friction coefficient distribution that can be selected as appropriate to suit the grinding work conditions and high pressure resistance. .

That is, the present invention relates to a metal processing agent, and further aims to provide an aqueous metal processing agent that is excellent in KFi workability and rust prevention ability.

Examples of the polyamine having at least two primary or secondary amino groups in the molecule, which is a raw material component of the polyaminoamine (11) compound used in the present invention, include the following.

Ethylenecyamine, propylene diamine, butylene diamine, hexamethylene diamine, trimethylhexamethylene diamine, piradzine, 1,18-diami24
-Aonomethyloctane, iminobisfτnruamine,
Methyliminobispropylamine, N-alkylpropylenediamine, xylylenediamine, diaminocyclohexane, bis(aminomethyl)cyclohexane, inphoronediamine, bis(aminocyclohexyl)methane,
diethylenetriamine, N-aminoethylbi-2-radine,
triethylenetetramine, tetraethylene R-antaban,
R-ntaethylenehexamine, 3-azahexane-1,6
-diamine, 4.7-cyazabucan-1,10-diamine, 4.7.11-) diazatetradecane-1,14
- selected from the group such as cyano, 4,8.11, 15-tetraazaoctadecane-1,18-diamine, 4.8,12.16-tetraazanonadecane-1,19-diamine, etc. alone or It is a mixture.

Examples of these are acrylic acid, methacrylic acid and their methyl, ethyl, propyl and butyl ester derivatives.

This vinyl monocarboxylic acid can be used in combination with the polycarboxylic acid, and such usage is an excellent method for imparting synergistic properties.

The organic polycarboxylic acid having at least two carboxyl groups in the molecule used in the present invention is a di- or tribasic polycarboxylic acid having 4 to 54 carbon atoms represented by formula 12). , R, (-COOH)n・f21 (R3 is a di- or trivalent saturated or unsaturated aliphatic group or alicyclic group, aromatic group, alkyl aromatic group, halodane-substituted aliphatic group or aromatic group , where n is 2 or 3
(representing an integer of ) Examples of these include:

Succinic acid, adipic acid, azelaic acid, henananotic acid,
P-decanoic acid, isophthalic acid, terephthalic acid, hydrogenated inoheptalic acid, hydrogenated terephthalic acid, halodanated isophthalic acid, halodanated terephthalic acid, maleated fatty acid, long chain dibasic acids commercially available from Okamura Oil Co., Ltd. These include carboxylic acids with 21 carbon atoms, polymerized fatty acids, and styrenated polymerized fatty acids commercially available from Westpaco, and also include ester derivatives thereof.

These polycarboxylic acids do not need to be used alone, and may be used as a mixture, or even in combination with the vinyl monocarboxylic acid, which is used in the present invention. A monocarboxylic acid is a synthetic or natural aliphatic or aromatic monocarboxylic acid, which has no practical use in both single components and natural sources that exist as purified or mixed components. , the following examples can be cited:

Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, casillonic acid, enanthic acid, caprylic acid, largonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, hantadecanoic acid, zolmitic acid, heptadecane Acid, stearic acid, linoleic acid, lysyllic acid, lysyllic acid, nonadecanoic acid, arachidic acid, heicosanoic acid, behenic acid, erucic acid, tricosanoic acid, lignocerin, natural vegetable oil fatty acid, fish oil fatty acid, animal oil and fat protection, benzoic acid , bratacharybutyl, hydroxybenzoic acid, etc., and their ester derivatives.

The blending proportions of polycarboxylic acid and monocarboxylic acid in the vinyl monocarboxylic acid and vinyl monocarboxylic acid as constituent components of the polyaminoamino compound are as follows.

m When using polyamine and vinyl monocarboxylic acid or polycarboxylic acid, the amount of vinyl monocarboxylic acid or polycarboxylic acid is 0.1 to 1 per mol of polyamine.
It is in the range of 0 g equivalent, preferably between 0.5 and 1.5 equivalent.

(2) In the case of polyamine, vinyl monocarboxylic acid, or polycarboxylic acid and monocarboxylic acid, the amount of vinyl monocarboxylic acid or polycarboxylic acid is in the range of 0.1 to 1.9 g, preferably 0.1 to 1.9 g per mol of polyamine.
Fio, in the range of 5 to 1.5 equivalents, and the monocarboxylic acid is in the range of 0.01 to 10 g equivalent, preferably in the range of 0.1 to 1 equivalent, and per mole of polyamine. , the total equivalent of vinyl monocarboxylic acid or polycarboxylic acid and monocarboxylic acid is 0.5 to 2
It is blended within the equivalent range.

If the tubing for the polyamine is less than this range,
Nine aminoamide compounds, which have little effect on the important properties of metal processing agents, namely machinability and grindability, are
On the other hand, if the amount exceeds these ranges, the polyaminoamino compound will have a high viscosity or will become infusible during the synthesis reaction, resulting in a so-called phosphorized state, making it difficult to use the desired substance that can be diluted with water. It becomes impossible.

The equivalent weight of polycarboxylic acid is the molecular weight per carboxyl group, and the equivalent weight of vinyl monocarboxylic acid is equivalent to half the molecular weight due to its reactivity with polyamines.

The vinyl monocarboxylic acid or polycarboxylic acid used as a raw material for the polyaminoamide compound has an influence on its properties as a metal processing agent depending on its molecular weight K. That is, in general, high molecular weight materials tend to contribute to frictional properties, while low molecular weight materials tend to contribute to water dilutability and pressure resistance.

Similarly, in the case of monocarboxylic acids, it is affected by the size of its molecular weight. In other words, roughly! .

High molecular weight materials tend to contribute to frictional properties, while low molecular weight materials tend to contribute to water dilutability and pressure resistance.

Therefore, by selecting the type and type of vinyl monocarboxylic acid or polycarboxylic acid and monocarboxylic acid, a polyaminoamide compound with excellent water dilutability can be obtained.
Additionally, the aqueous metalworking agent may have any properties suitable to the conditions of the metalworking operation.

The polyaminoamide compound of the present invention is originally a highly hydrophilic substance and can be easily dispersed in water, but the state of the aqueous dispersion differs depending on the type. That is, it shows various states such as emulsion, colloidal dispersion, and liquid solution. As a metal processing agent, its effectiveness is not determined by its state of nK, and therefore it cannot be limited by its dispersion state, but it is sometimes used in dispersions with strong chikuntropic properties, and in water. There are some products whose viscosity is difficult to reduce even when diluted, and some that separate from water over time. It is possible to improve the dispersibility and dilutability with water.

The polyaminoamide compound or its salt of the present invention can be directly dispersed in water and used as a metal processing agent. It can also be used in combination with processing agents or their components.

The polyaminoamide compound of the present invention can be synthesized by a conventional method, and the outline thereof is as follows.

(1) When vinyl monocarboxylic acid is used, the polyamine, acid compounds, and water equivalent to 50% of the total charge are placed in a reaction vessel equipped with a stirring device, a heating device, an inert gas inlet device, a moisture condenser, and a trap device. Prepare it. While stirring this, the vinyl monocarboxylic acid charged in the dropping funnel is added dropwise while avoiding rapid heat generation. After the addition is complete, the mixture is stirred for 2 hours under reflux of water. Next, the reaction is completed by gradually heating and distilling off water while maintaining the temperature between 180'C and 220'C for 1 to 2 hours.If necessary, unreacted components are distilled off under reduced pressure. In this way, the desired polyaminoamide compound is obtained.

(2) When vinyl monocarboxylic acid is not used, a polyamine and acid compounds are placed in a reaction vessel similar to m above. Gradually heat this while stirring until the temperature reaches 180℃.
The reaction is maintained for 1 to 2 hours between 'C and 220''C to complete the reaction. If necessary, unreacted components are distilled off under reduced pressure to obtain the target polyaminoamide compound.

The above reactions (1) or (2) are all carried out under inert gas flow to prevent oxidation by air, and the water or alcohol produced during the reaction is passed through a condenser and drained into the trap below. .

Next, a more specific explanation will be given using examples.

Examples 1 to 14 Polyaminoamide compounds were prepared according to the synthesis methods (0 and (2) above) by changing the types and amounts of polyamine, vinyl monocarboxylic acid, polycarboxylic acid, and monocarboxylic acid as shown in Table 1. Examples 3.4 and 5 were made according to the synthesis method (1) above, and all others were made according to the synthesis method (2) above.

Examples 15 to 36 The polyaminoamide compounds synthesized in Examples 1 to 14 were used as they were, or in order to improve fluidity, they were made into KIJ phosphate and diluted with water, which is a commonly used rust inhibitor. When triethanolamine was combined with triethanolamine, its performance as a metal processing agent, that is, its friction properties, pressure resistance, and rust prevention properties were investigated, and the results shown in Table 2 were obtained.

The friction, pressure resistance, and rust prevention tests here are as follows.

+1) Jil I friction property: The coefficient of friction (μ) is measured at 5°C using a Soda type ■ type Soshi oil tester.

(2) Pressure resistance: according to Soda Nishi-ball lubricant tester)) 21
The pressure resistance (Kg/CrrL2) is measured at 10 rpm.

(31 Rust prevention: After immersing the dry cutting chips of the casting in an aqueous solution of a polyaminoamide compound, drain the liquid and put it in a Petri dish, and observe the rusting state by waiting KU in an atmosphere of I″C1 humidity of 80%. Evaluation is performed using the Fien point method, and a score of 10 is given to a product with no rust at all.

Reference Example Tests similar to those in the Examples were conducted on a known metal processing agent, triethanolamine sepatic acid salt, and two types of commercially available A%B metal processing agents.The results are shown in Table 2.

As is clear from Table 2, the water-based metal processing agent made from the polyaminoamide compound or its salt of the present invention has superior rust prevention ability compared to conventional products, while the coefficient of friction is distributed over a wide range, making it less susceptible to rust. At the same time, a product exhibiting high pressure resistance was obtained, and it can be seen that this makes it a versatile metal processing agent that can be applied to a wide range of applications such as cutting agents, abrasive agents, quenching, and plastic deformation processing.

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Claims (1)

[Scope of Claims] (1) (a) A small number of primary or secondary amino groups in the molecule;
An aqueous metal processing agent containing a polyamino εr compound or a stage thereof formed by heat-reacting in a range of 11 g equivalent. (2) The polyamine having -R or a secondary amino group in the molecule is ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, trimethylhexamethylene diamine, piperazine, 1,8-diamino-4-aminomethyloctane, iminobispropylamine, methyliminobispropylamine, N-alkylpropylenediamine, xylylenediamine, diaminocyclohexane, bis(aminocyclohexyl)methane, diethylenetriamine, N-aonoethylpyrazine, triethylenetetramine, tetraethylene diamine, Interethylenehexamine, 3-azahexane-1,6-
diamine, 4+7-') azadecane-1,10-diamine, 4,7,1]-) diazatetradecane-1,14-
Cyan, 4.8111, 15-tetraazaoctadecane-1,18-diamine, 4+L12+16-tetraazano-nadecane-1,19-diamine, either singly or as a mixture. The water-based metal processing agent according to item 1. (3) Vinyl monocarboxylic acid is represented by ⑐m, CH
,: c-co○R11... (1) The aqueous metal processing agent according to claim 1, which is acrylic acid (representing an alkyl group up to 1), methacrylic acid, and ester derivatives thereof. (4) The organic polycarboxylic acid having at least two carboxyl groups in the molecule is a dibasic or tribasic polycarboxylic acid having 4 to 54 carbon atoms and represented by formula (2). Aqueous metal processing agent according to scope 1. R3(-C00R4)n...(2) (R, is a di- or trivalent saturated or unsaturated aliphatic group or alicyclic group, aromatic group, alkyl aromatic group, halodane-substituted aliphatic group) (5) the aqueous metal according to claim 1, wherein the polyaminoamine P compound is a salt; (5) the polyaminoamine P compound is a salt; processing agent. (6) (IL) has a small number of primary or secondary amino groups in the molecule, component (1)) is in the range of 0.1 to 1.9 g equivalent, and component (C) is in the range of 0.01 to 10 g equivalent. range, and the total equivalent of component (1) and component (C) is (), which is obtained by heating reaction in the range of 5 to 2.
A water-based metal processing agent containing IJ Aminoa (y compound or its salt). (7) The polyamine having a primary or secondary amino group in the molecule is ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, trimethylhexamethylene diamine. , pizladine, 1,8-diamino-4-aminomethyloctane, iminobispropylamine, methylinobisderopylamine, N-alkylpropylenediamine, xamethylenediamine, riaminocyclohexane, bis(aminocyclohexyl)methane,
diethylenetriamine, N-aminoethyl bigrazine,
triethylenetetramine, tetraethylene is tamamine,
hantaethylenehexane, 3-azahexane-1,6
-diamine, 4.7-cyazadecane-1. lO-diamine, 417111-) 1 noazatetradecane-1,
14-diamine, 4.8,11.15-tetraazaoctadecane-1,18-diamine, L8ejz+16-tetraazanonadecane-1,19-liamine, singly or in mixtures. Aqueous metal processing agent according to item 6. (8) Vinyl monocarboxylic acid is represented by formula (1),
CH,: C-C0OR corridor... (1)
7. The aqueous metal working agent according to claim 6, which is acrylic acid, methacrylic acid (representing an alkyl group up to) and ester derivatives thereof. (9) Claims in which the organic polycarboxylic acid having at least two carboxyl groups in the molecule is a dibasic or tribasic polycarboxylic acid having from 4 to 100 carbon atoms and represented by formula (2). Aqueous metal processing agent according to item 6. R3(-000R4)n...(2) (R3 is a di- or trivalent saturated or unsaturated aliphatic group or alicyclic group, aromatic group, alkyl aromatic group, halodane-substituted aliphatic group or aromatic group group, R4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3)
Aqueous aqueous according to claim 6, wherein the α1 monocarboxylic acid is an alkyl aromatic monocarboxylic acid (representing an aliphatic saturated or unsaturated fatty acid having 1 to 22 carbon atoms and a group represented by formula 13)) Metal processing agent. 0υ The aqueous metal processing agent according to claim 6, wherein the polyaminooxide compound is a salt.