JPH01201400A - Water-soluble metal working oil - Google Patents

Abstract

PURPOSE:To improve the antiseptic property of a water-soluble metal working oil, by mixing it with a particular arom. diamine or alicyclic diamine in a particular amt. CONSTITUTION:This water-soluble metal working oil contains an arom. diamine of formula I and/or an alicyclic diamine of formula II and/or an arom. diamine of formula III and/or an alicyclic diamine of formula IV, wherein the weight ratio of the total amt. of the diamines of the formulae I and II to that of the diamines of the formulae III and IV is 90:10-10:90 and the total amt. of the diamines of the formulae I-IV is 1-30wt.% of the oil. Examples of the diamine of the formula I include m-xylenediamine, those of the diamine of the formula II include 1,3-bis(aminomethyl)cyclohexane, those of the diamine of the formula III include 4,4'-diaminodiphenylmethane, and those of the diamine of the formula IV include 4,4'-diaminodicyclohexylmethane.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a water-soluble metal working oil that is used when processing metal materials such as cutting, grinding, rolling, punching, drawing, etc. This invention relates to an excellent and improved oil agent.

(Prior art) There are two types of water-soluble metalworking fluids, such as soluble type and emulsion type, but all of them have surfactants, rust preventives, lubricating oils, etc. as their main ingredients. It has been recognized that such oils have the disadvantage of being susceptible to spoilage during use, since they are also suitable nutrient sources for bacteria and mold.

(Problem to be Solved by the Invention) Conventionally, as a preservative measure to deal with such drawbacks, methods of adding various preservatives have been used. For example, it is known to add phenolic compounds, formaldehyde donor compounds, cationic surfactants, heavy metals, and the like. However, if such preservatives are added in large enough quantities to completely inhibit bacteria and mold, the side effects may impair emulsion stability and rust prevention, or increase irritation to the human body. Therefore, it has been difficult to take complete antiseptic measures by adding preservatives.

On the other hand, the soluble type of water-soluble metalworking oil is used as a rust preventive agent, and also when the alkalinity of the oil is kept within an appropriate range (pH 8).
~10.5) Various amines such as alkanolamine, cyclohexylamine, and dicyclohexylamine are used as alkaline substances to maintain the temperature of It is common that soaps are used to emulsify lubricating oils and also contain some free amines as alkaline substances.

Normally, if a large amount of MR1 amine is contained, will the alkalinity be large? Although this can suppress rot, it also increases irritation, which is undesirable.

As mentioned above, in the conventional techniques, it has been difficult to completely suppress spoilage using both the method of adding preservatives and the method of containing a large amount of free amine.

Therefore, an object of the present invention is to provide a water-soluble metalworking fluid with improved antiseptic properties.

(Means for Solving the Problems) In order to achieve the above object, the present inventors studied the characteristics of various amines, and found that there are a wide variety of amines, including monoamines, diamines, triamines, etc. Each type is classified into aliphatic, aromatic, and alicyclic types, and each has different alkalinity, irritation to the human body, and action against bacteria and mold. As a result of researching the synergistic effects of combinations of these various amines, we found that by combining specific amines in specific ratios and containing specific amounts in water-soluble metalworking fluids, alkalinity can be kept within an appropriate range. Moreover, it was newly learned that spoilage can be significantly suppressed, leading to the present invention.

That is, the present invention contains the following (1) in a water-soluble metalworking fluid.
Contains an aromatic diamine represented by the formula and/or (2) an alicyclic diamine represented by (2) and (3) an aromatic diamine represented by (2) and/or (4) an alicyclic diamine represented by (2). , the total amount of diamines of formulas (1) and (2) above, and (3
) and (4) The weight ratio of the total amount of diamine 2 is 90
: 10 to 1°: within the range of 90, and (1),
The present invention relates to a water-soluble metalworking fluid characterized in that the total amount of diamines of formulas (2), (3), and (4) accounts for 1 to 30% by weight in the fluid.

That is, the present invention deals with specific amines (1), (2),
The diamines represented by formulas (3) and (4) are used in combination at the specified ratio, and the specified amount is contained in the water-soluble metal working fluid.

The weight ratio of the total amount of diamines of formulas (1) and (2) to the total amount of diamines of formulas (3) and (4) is 90:1.
0 to 10: If the total amount of diamines (3) and (4) is less than the range of 90, the purpose of inhibiting spoilage will not be achieved, and if it is more than this range, it will not be possible to stably dissolve and disperse the diamines in the oil. Both are difficult and inappropriate.

If the total amount of diamines (1), (2), (3) and (4) is less than 1 to 30% by weight in the oil, there is no spoilage inhibiting effect, and if it is more than this, it may cause irritation. becomes strong, which is also inappropriate. In addition, (1), (2
), (3) and (4) diamines are respectively (1) metaxylene diamine (MXDA) (2)
1.3-bis(aminomethyl)cyclohexane (BM
MC) (3) 4.4'-diaminodiphenylmethane (DADPM) (4) 4.4'-diaminodicyclohexylmethane (DADCM).

(Effect) As a result of research, it has been found that only a combination of diamines with a specific molecular structure and a specific ratio exhibits the effects of the present invention, but the reason for this has not been completely confirmed. is generally considered to be as follows.

Unlike commonly used alkanolamines, dicyclohexylamine, ethylenediamine, etc., the amine used in the present invention has large organic groups (hydrocarbon groups) and inorganic groups (amino groups, hydroxyl groups) in the molecule, and There is a balance between the two. Inorganic/organic ratio I10
[Calculated using the method of Organic Conceptual Diagram by Yoshio Koda, published by Sankyo Publishing], (1) is 155 / 160 = 1.0, (2
) is 150 /160 = 0.94, (3) is 170
/260 = 0.65, (4) is 160 /260 =
0.62, whereas triethanolamine is 370/120 = 3.1, jetanolamine is 90/240 = 0.38, and ethylenediamine is 140
/40=3.5.

In other words, the diamines (1) and (2) have a good balance, and the diamines (3) and (4) have particularly large organic and inorganic groups. ) and (3) and/or (4)
By mixing diamines of the formula, a well-balanced mixed amine with large organic and inorganic groups can be obtained.

On the other hand, it is known that the cell membrane and cell wall that constitute the bacterial body have both hydrophilic and hydrophobic parts, and the interaction between this hydrophilic part and the inorganic group of the amine used in the present invention due to polarity. It is highly conceivable that the hydrophobic moiety and the organic group of the amine have an interaction force due to van der Waals force, and that the adsorption effect is significantly stronger and more balanced than that of conventional amines. It is a place.

The present invention can be applied to cutting fluids of all types, soluble type and emulsion type; however, as an example, in the soluple type, caprylic acid, pelargonic acid, and lauric acid are used as surfactants (emulsifiers). acid,
Aniline activators such as fatty acid alkali salts of fatty acids such as oleic acid and ricinoleic acid, alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine, and inorganic alkalis such as potassium hydroxide and sodium hydroxide, polyoxyethylene - Nonionic activators such as sorbicun monolaurate and polyoxyethylene oleyl ether are used, and petroleum sulfonates such as sodium petroleum sulfonate and fatty acid esters such as sorbitan monooleate are used as rust preventive agents. Then, these components are mixed with water, dispersed and dissolved, and the amine combination of the present invention is added, and if necessary, an antifoaming agent, a non-ferrous metal corrosion inhibitor, a bactericide, an inorganic salt, and a glycol are added. It is also appropriate to add other additives such as. In the emulsion type, a lubricating oil such as mineral oil or ester oil is used as a base oil, and the above-mentioned surfactant (emulsifier) and rust preventive agent are added and dispersed in the base oil, and then the amine combination of the present invention is added. In addition,
In addition, the other additives mentioned above are added as necessary.

(Example) Next, the present invention will be explained with reference to Examples and Comparative Examples.

Examples 1 to 13 and Comparative Examples 1 to 6 in Table 1 are soluble type examples, Examples 14 to 24 and Comparative Examples 7 to 12 are emulsion type examples, m composition (ffiffi%), properties, and test results. showed that. The respective manufacturing methods for Example 1 and Example 14 are as follows.

Equilibrium open↓ 5% by weight of pelargonic acid, 5% by weight of lauric acid, 10% by weight of ricinoleic acid, and 20% by weight each of jetanolamine and triethanolamine were stirred at 80'C and mixed uniformly. Next, 5% by weight of sodium petroleum sulfonate, 10% by weight of sorbitan monooleate, and 5% by weight of polyoxysorbitan monolaurate E020 were added.
The mixture was stirred at 0 to 80°C to uniformly combine the mixture.

Next, this mixture was cooled to 50°C, and while maintaining the temperature at 40 to 50°C, 15% by weight of water was added with stirring and mixed uniformly. Finally, MXDA 1% by weight, DADPM 4
% by weight was added and stirred to mix uniformly.

5% by weight of caprylic acid, 3% by weight of lauric acid, 1% by weight of oleic acid and 1 part of 20% by weight of mineral oil were stirred at 80° C. and mixed uniformly. Next, add 2% by weight of potassium hydroxide as a 50% aqueous solution and stir, and then add 3% by weight of noethanolamine and stir to make it homogeneous. It came together.

Next, add 5% by weight of sodium petroleum sulfonate, 5% by weight of sorbitan monooleate, 5% by weight of polyoxyethylene oleyl ether E05 mol Jll'& 3II, and the remainder of mineral oil, and stir at 60-80°C to mix uniformly. . The mixture was cooled to 50°C and
6% by weight of CADCM was added and stirred to mix uniformly.

Examples 2 to 13 and Comparative Examples 1 to 6 were produced in the same manner as Example 1, and Examples 15 to 24 and Comparative Examples 7 to 12 were produced in the same manner as in Example 12, and were used as samples (undiluted solutions), respectively.

The following tests A to H were conducted for each sample.

Test results (effects of the invention) were obtained for A to G as shown in Table 1, and for H as shown in the same section.

A. Stability of stock solution 100 g of each sample (stock solution) was collected in a 140 ml glass bottle with a lid, and this was left to stand in a constant temperature bath at 50''C for one week, and the state of separation thereafter was observed with the naked eye.

○: No separation without change) ×: Separation B, diluted liquid appearance Each sample (diluted liquid) (Examples 1 to 13, Comparative Examples 1 to 6 are 1
100 g of 2 wt % water diluted solution (Examples 14 to 24 and Comparative Examples 7 to 12 are 2 wt % water diluted solution, the same applies hereinafter)
The sample was collected in an mQ graduated cylinder, and the appearance was visually observed.

S: Transparent liquid E: Milky white emulsion C0pl+ 9H of each sample (diluted solution) was measured using a pH meter.

D. 25ml of each rust prevention sample (diluted solution) was mixed with 20 pieces of cast iron FC-20 chips.
Betori colander with lid (diameter 60mm x height 15mm)
) and allowed to stand for 15 minutes. The diluted solution was then decanted, covered and left at room temperature for 48 hours. Between 8゜12
The state of rusting after 24.48 hours was observed with the naked eye.

○: No rusting B: Approximately 10% rusting △: Approximately 50% E. Putrefaction test (ASTM-D-3946 r Test method for evaluating antibacterial properties of water-soluble metal working fluids) 100 g of each sample (diluted solution) was heated at 20 O n/! with a cotton plug!
Collected in an Erlenmeyer flask and activated by adding trypto soy broth medium and glucose peptone medium in advance, 10 g of putrid liquid, 3 g of lubricating oil, and L of cast iron FC-20 chips.
og was added and cultured with shaking at 30°C for 2 weeks, and the number of viable bacteria (cells/mf) in the subsequent diluted solution was measured for aerobic bacteria, anaerobic bacteria, mold, and yeast.

In addition, 10 g of putrefaction liquid was additionally added during the first week.

F. 3 of each sample (diluted solution) of Grinding Test Examples 1 to 13 and Comparative Examples 1 to 6
0I! ．． was placed in the coolant tank of the Hitachi surface grinder, and while circulating and refueling, a grinding test was conducted under the following conditions, and the grinding ratio (
The amount of cut material ff1g/wear amount of the grindstone g) was measured.

Work material: 5UJ-2 bearing steel grindstone: HA-60-J Grinding speed: 2000m/min Grinding allowance: 20/1000 G. Cutting test examples 14 to 24 and comparative examples 7 to 12 samples (diluted liquid)
While refueling the upright drilling machine, a tapping test was conducted under the following conditions, and the cutting torque (kg) was measured using a cutting torque meter.
-cm) was measured.

Tap (tool): Hand tap M2OX2.5 work material
: 545C diameter 30mm x height 30mm Cutting speed:
6.9m/min Cutting length: 30mm Prepared hole: Diameter 17.5mu+ Lubrication: 600ml/min Manual lubrication H
0 On-site test H-1 Grinding test The sample (diluted solution) of Example 1O and a 2% diluted solution of the conventional soluble type grinding fluid commercial product M were put to practical use in the grinding process of automobile parts under the following conditions at an automobile factory site.

In Example 10, no decrease in pa+ or generation of bad odor was observed even after 6 months of use, and the product was used normally.

Commercial product M was used for one month, and a decrease in pH and generation of a bad odor were observed, so the liquid was replaced.

Processing method: Two cylindrical grinding processed parts: Camshaft tank capacity: 5 oz About the sample of H-2 cutting test Example 21 (3% diluted liquid) and the 3% diluted liquid of commercially available emulsion type cutting fluid N from automobile factory It was put to practical use in the cutting process of automobile parts under the following conditions at the site.

Regarding Example 21, no decrease in pH or generation of bad odor was observed even after one year of use, and it was used normally.

Commercial product N was used for two months, and a decrease in pH and generation of a bad odor were observed, so the liquid was replaced.

Processing method Drill and reamer using Nidor transfer machine
, tapped processing parts: Engine parts Tank capacity: 2000 ff (Effects of the invention) The water-soluble metalworking oils of the present invention shown in Examples 1 to 24 showed no viable bacteria in the putrefaction test compared to the oils of Comparative Examples 1 to 12. The number of anaerobic bacteria, especially the number of anaerobic bacteria that cause bad odors, is extremely low (it was confirmed that the antiseptic properties are very good).

This is supported by the fact that in field tests comparing the oils of Examples 10 and 21 with commercially available grinding oils and cutting oils, the antiseptic properties were significantly superior, and the lifespan until fluid replacement was six times longer. It is being

In addition, the water-soluble metal working fluid of the present invention has excellent rust prevention properties and alkalinity (PT) within an appropriate range, and has satisfactory grinding performance and cutting performance. It has been confirmed that this has been achieved.

Claims (1)

[Scope of Claims] 1. An aromatic diamine represented by the following formula (1) and/or an alicyclic diamine represented by the following formula (2) and an aromatic represented by the formula (3) in a water-soluble metalworking fluid. Contains group diamine and/or alicyclic diamine represented by formula (4), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) ▲Mathematical formulas, There are chemical formulas, tables, etc.▼(3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(4) The total amount of diamine in formulas (1) and (2) above, and (3)
) and the total amount of diamine of formula (4) in a weight ratio of 90:
Within the range of 10 to 10:90, and (1), (2)
, (3) and (4) in a total amount of 1 to 30% by weight of the oil.