JPH06287589A - Water-soluble lubricating rust-preventive oil for plastic working - Google Patents

Abstract

PURPOSE:To obtain a water-soluble lubricating oil excellent in lubricating properties, rust-preventive power, workability, etc., by using a salt of a specified alkylthiopropionic acid with an alkanolamine as the essential component. CONSTITUTION:A salt of a carboxylic acid of formula I (wherein R<1> is 6-22C alky; and R<2> is H or methyl) with an amine of formula II [wherein X<1> and X<2> are each H, 1-3C alkyl or hydroxyalkyl of the formula: (CH2),-OHz (z) is 1-3; and (y) is 0-2] is produced. The obtained salt as an essential component is mixed with optional additives such as a pH adjuster, an oiliness improver and an extreme-pressure additive to produce the objective oil. Examples of the carboxylic acids include hexylthiopropionic acid and octylthiopropionic acid. Examples of the amines include monoethanolamine and diethanolamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble lubricating rust preventive oil agent for plastic working.

[0002]

2. Description of the Related Art Steel sheets produced by steel makers are generally coated with various rust preventive oil agents at the time of shipment. When performing plastic working of these steel sheets, such as pressing and drawing, apply the lubricant for plastic working directly to the steel sheet coated with the rust preventive agent or after removing the rust preventive agent We are working.

Products after plastic working are often stored in a state where the above-mentioned lubricant is applied. In this case, among the lubricating oil agents, an oil agent having both lubricity and rust preventive property, that is, a lubricating rust preventive oil agent for plastic working is generally used. This lubricant anti-rust oil is usually used for plating, chemical conversion treatment,
It is removed when applying surface treatment such as painting.

Such a lubricating rust preventive oil agent is disclosed in JP-A-3-6.
8697, JP-A-59-227991 and other aqueous type (water-soluble) oil agents, and JP-A-3-2124
The oil-based (non-water-soluble) oil agents disclosed in Japanese Patent Publication No. 95, etc. are roughly classified.

Of these, the water-based oil agent has the advantage that it can be easily removed by means such as washing with water after the plastic working, but it generally has poor persistence on the metal surface and has a low rust preventive property. Therefore, when the workpiece is to be stored for a long time after the plastic working, it is necessary to remove the water-based oil agent and then apply a new rust preventive oil agent.

[0006] Further, the oil-based oil agent has an advantage that it is excellent in remaining property on the metal surface and has a high anticorrosive ability. However, when the oil-based oil agent is removed for surface treatment or the like, a degreasing step is required. The work called is required. In the degreasing step, an alkaline degreasing agent containing sodium hydroxide, potassium hydroxide, etc., a fluorine-based solvent such as CFC-113 (CCl ₂ F-CClF ₂ ), a chlorine-based solvent such as 1,1,1-trichloroethane, or Hydrocarbon-based solvents such as hexane are often used.

However, when an alkaline reagent is used, it is necessary to neutralize the wastewater in advance before the wastewater treatment such as the activated sludge treatment, and the economical addition required for the wastewater treatment is great. In addition, the inorganic alkali contained in the degreasing agent easily causes deterioration of the metal surface. Many of the fluorine-based solvents and chlorine-based solvents are designated as ozone depleting substances in the Montreal Protocol (established in 1987), and at the Conference of the Parties to the Protocol held in November 1992, these It has been adopted to abolish the production and use of substances by the end of 1995.

Moreover, since chlorine-based solvents have a larger specific gravity than water and contain many substances that are harmful to living things, if they are leaked to the outside due to mishandling or equipment failure,
It has a negative impact on soil and groundwater systems. Further, a hydrocarbon solvent such as hexane has a problem of exhibiting extremely high flammability.

[0009]

As described above, the water-based oil agent has a problem of inferior rust preventive ability, and the oil-based oil agent has various problems associated with the degreasing process. As a lubricating rust preventive oil agent, it has not been fully satisfactory.

In view of the above-mentioned conventional circumstances, the present invention provides a water-soluble lubricating rust preventive oil agent for plastic working which has excellent lubricity and long-term rust preventive ability, and can be easily washed and removed from a metal surface by means such as washing with water. Is intended to provide.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, found that a water-soluble lubricating rust preventive oil agent using a salt of a specific carboxylic acid and a specific amine was used. The inventors have found that they have high lubricity suitable for plastic working, long-term rust preventive ability, and excellent cleaning and removal properties, and have completed the present invention.

That is, the present invention provides the following formula: (Wherein R ¹ is an alkyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group), and the following formula; [Wherein, X ¹ and X ² are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group represented by — (CH ₂ ) _z —OH (z is 1 to 3), and y is 0 to 2 The present invention relates to a water-soluble lubricating rust preventive oil agent for plastic working, which comprises a salt with an amine represented by the following formula as an essential component.

[0013]

In the carboxylic acid represented by the formula (I) used in the present invention, the alkyl group (R ¹ ) has 6 to 22 carbon atoms, particularly preferably 8 to 22 carbon atoms. When the carbon number is less than 6, it is difficult to obtain good lubricity, and when the carbon number exceeds 22, the solubility in water remarkably decreases.

Examples of such carboxylic acids include hexylthiopropionic acid, hexylthio-2-methyl-propionic acid, octylthiopropionic acid, octylthio-2-methyl-propionic acid, 2-ethylhexylthiopropionic acid, (2 -Ethylhexyl) thio-
2-methyl-propionic acid, decylthiopropionic acid,
Decylthio-2-methyl-propionic acid, dodecylthiopropionic acid, dodecylthio-2-methyl-propionic acid, tetradecylthiopropionic acid, tetradecylthio-2-methyl-propionic acid, hexadecylthiopropionic acid, hexadecylthio-2- Methyl-propionic acid, octadecylthiopropionic acid, octadecylthio-2-methyl-propionic acid, eicosylthiopropionic acid, eicosylthio-2-methyl-propionic acid, docosylthiopropionic acid, docosylthio-2-methyl-
Examples include propionic acid.

In the amine represented by the formula (II) used in the present invention, X ¹ and X ² are a hydrogen atom, an alkyl group or a hydroxyalkyl group, and the alkyl group or the hydroxyalkyl group has 1 carbon atoms, respectively. -3, particularly preferably 1-2. If the number of carbon atoms in these groups exceeds 3, water solubility will decrease and it will be difficult to obtain industrially.

Examples of such amines include monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1,3-propanediol and 2-amino-2-hydroxymethyl-amine. 1,
3-propanediol, 1-amino-2-ethyl-1,
Examples include 3-propanediol.

The salt in the present invention comprises a carboxylic acid represented by the formula (I) and an amine represented by the formula (II) in an amount of 50 to 1
By stirring and mixing at 20 ° C to cause a neutralization reaction,
Can be easily obtained. Here, the mixing molar ratio of the carboxylic acid and the amine is usually 1: 0.5 to 1.5, preferably 1: 0.7 to 1.3.

The water-soluble lubricating rust preventive oil agent for plastic working of the present invention contains the above-mentioned salt as an active ingredient, and if necessary, various additives such as a pH adjusting agent, an oiliness improver and an extreme pressure additive. , Rust preventives, antiseptic / mold preventives, etc. can be added within a range that does not impair various properties such as lubricity.

The water-soluble lubricating rust preventive oil agent for plastic working of the present invention is used as a solution (or dispersion) in which these components are usually dissolved (or dispersed) in water for plastic working of metal materials such as steel plates. To be done. In this solution (or dispersion), the concentration of the salt is usually 2 to 50% by weight, preferably 5 to 40% by weight, more preferably 7 to 30% by weight, further preferably 10 to 30% by weight. .

[0020]

The water-soluble lubricating rust preventive oil agent for plastic working of the present invention has excellent lubricity and long-term rust preventive ability, and because it is water-soluble, it can be easily removed from the metal surface by washing with water. Excellent workability and wastewater treatment. Also,
Since the salt has a sulfide bond in the molecule, it is more soluble in water than ordinary carboxylic acid soaps, so it can be stored at a high concentration and is also excellent in space saving during storage. .

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 24.4 g (0.4 mol) of monoethanolamine was added to 0.2 wt.
It was dissolved in 8 kg of ion-exchanged water and heated to 70 ° C.
To this solution, 87.3 g of octylthiopropionic acid
(0.4 mol) was added, and the mixture was stirred and mixed for 60 minutes for neutralization reaction. Ion-exchanged water was added to the obtained solution to make the total mass of the solution 1.12 Kg to obtain a 10 wt% aqueous solution of octylthiopropionic acid monoethanolamine salt,
This was designated as sample a.

Examples 2 to 8 The neutralization reaction was carried out in the same manner as in Example 1 except that the kinds of carboxylic acid and amine were changed to obtain 7 kinds of samples b to h shown in Table 1 below.

[0024]

[Table 1]

Comparative Example 1 A neutralization reaction was carried out in the same manner as in Example 1 except that butylthiopropionic acid was used as the carboxylic acid to obtain a 10% by weight aqueous solution of butylthiopropionic acid monoethanolamine salt. Sample i was used.

Comparative Example 2 0.8 kg of 16.0 g (0.4 mol) of sodium hydroxide
Was dissolved in ion-exchanged water, and the temperature was raised to 70 ° C. To this solution, 109.7 g of dodecyl thiopropionic acid (0.
4 mol) was added, and the mixture was stirred and mixed for 60 minutes for neutralization reaction. Ion-exchanged water was added to the obtained solution to give a total solution mass of 1.19 Kg to obtain a 10 wt% aqueous solution of sodium dodecylthiopropionate, which was designated as sample j.

Comparative Example 3 A neutralization reaction was carried out in the same manner as in Comparative Example 2 except that octadecylthiopropionic acid was used as the carboxylic acid to obtain a 10% by weight aqueous solution of octadecylthiopropionic acid sodium salt. And

Comparative Example 4 16.0 g (0.4 mol) of sodium hydroxide was added to 0.8 kg.
Was dissolved in ion-exchanged water, and the temperature was raised to 70 ° C. Add oleic acid [NAA-3 manufactured by NOF CORPORATION] to this solution.
4 "] 113.0 g (0.4 mol) was added, and the mixture was stirred and mixed for 60 minutes to cause a neutralization reaction. Ion-exchanged water was added to the obtained solution to make the total weight of the solution 1.22 Kg to obtain a 10 wt% aqueous solution of sodium oleate, which was designated as Sample 1.

Comparative Example 5 24.4 g (0.4 mol) of monoethanolamine was added to 0.2%.
It was dissolved in 8 kg of ion-exchanged water and heated to 70 ° C.
Add oleic acid [NAA manufactured by NOF CORPORATION] to this solution.
-34 "] 113.0 g (0.4 mol) was added, and the mixture was stirred and mixed for 60 minutes to cause a neutralization reaction. Ion-exchanged water was added to the obtained solution, and the total weight of the solution was adjusted to 1.37 Kg to obtain a 10 wt% aqueous solution of monoethanolamine oleate as a sample m.

Comparative Example 6 A commercially available water-insoluble plastic working oil (mineral oil + fatty acid system; stock solution) was used as sample n.

Comparative Example 7 A commercially available water-soluble plastic working oil agent (mineral oil + fatty acid alkali metal salt type; 10% by weight emulsion) was used as a sample o.

Comparative Example 8 Commercially available water-insoluble lubricating rust preventive oil agent (mineral oil + petroleum sulfonate)
(G) stock solution) was used as sample p.

Comparative Example 9 A commercially available water-soluble rust preventive oil agent (petroleum sulfonate + fatty acid alkali metal salt type; 10% by weight emulsion) was used as sample q.

With respect to the samples a to q of Examples 1 to 8 and Comparative Examples 1 to 9 described above, the lubricity test (test 1), the rust prevention test (test 2), and the detergency test (test) were carried out by the following methods. I went to 3). The results are shown in Table 2 below. In addition, in the same table, as a blank test (Reference Example 1), the result of the test without using the sample is also shown.

<Test 1: Lubricity test (pull-out test)>
A test piece (molten zinc plated steel plate GA60 / 60: test piece size 270 mm × 30 mm × 0.8 mm) was dipped in the sample for 2 minutes and then dried in a warm air dryer at 60 ° C. for 20 minutes.
The dried test piece was sandwiched in a one-stage bead-type pull-out tester shown in FIG. 1, pulled upward at a speed of 50 mm / min, and the maximum load (Kgf) during pulling was obtained to evaluate the lubricity. The judgment criteria are as follows. ◎: Maximum load less than 190Kgf ○: Maximum load 190Kgf or more to less than 220Kgf △: Maximum load 220Kgf or more to less than 240Kgf ×: Maximum load 240Kgf or more

In FIG. 1, reference numeral 1 denotes a concave mold having a concave groove portion 11 having a width of 13 mm and a depth of 10 mm at the center in the vertical direction, and 2 denotes a hemispherical shape corresponding to the concave groove portion 11 (al 5).
mm) with a convex strip 21. Both molds 1, 2
The test piece 3 interposed between the two washer W1 having a thickness of 1 mm, by means of bolts V1 (V2) and nuts N1 (N2).
After being sandwiched through (W2) as shown,
It is pulled upward at the above speed. The arrow x indicates the pulling direction.

<Test 2: Anticorrosion test (JIS K 22
46)> A test piece (cold rolled steel plate SPCC: test piece size 270 mm × 30 mm × 0.8 mm) was immersed in the sample for 2 minutes, and then dried in a warm air dryer at 60 ° C. for 20 minutes.
The dried test piece was exposed to an atmosphere of a temperature of 49 ± 1 ° C. and a humidity of 90% for 240 hours and 720 hours. The area of rust generated after exposure was measured to determine the rust prevention property. The judgment criteria are as follows. ◎: No rusting ○: Rusting less than 2% of the surface area Δ: Rusting 2% or more and less than 10% of the surface area ×: Rusting 10% or more of the surface area

<Test 3: Detergency test> A test piece coated with a sample (cold rolled steel plate: test piece size 270 mm x 30 mm x
0.8 mm) was exposed in an atmosphere of a temperature of 49 ± 1 ° C. and a humidity of 90% for 720 hours. After the exposure, the steel plate was allowed to stand in water at room temperature for 60 seconds and then washed with running water for 60 seconds. The washability was evaluated by the size of the wetted area after washing with running water. The judgment criteria are as follows. ○: The sample could be removed (wetted surface) ×: The sample could not be removed (some parts repel water)

[0039]

[Table 2]

As is clear from Table 2 above, according to the water-soluble lubricating and rust preventive oil agent of the present invention, excellent plasticity and excellent long-term lubricity can be obtained by a single application during plastic working such as pressing and drawing. It can be seen that the rust prevention effect is obtained, and that it can be easily removed only by washing with water when the surface treatment such as coating is performed, and the handleability is excellent. On the other hand, commercially available water-insoluble or water-soluble plastic working oils and the like are markedly inferior to any of these characteristics.

[Brief description of drawings]

[Fig. 1] Single-stage beam used for lubricity test (pull-out test)
It is a longitudinal cross-sectional view showing a do-type pull-out tester.

[Explanation of symbols]

 1 Concave mold 2 Convex mold 3 Test piece x Drawing direction

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C10N 30:12 40:24 Z 8217-4H (72) Inventor Nobuhiko Shizu 9 Ikekai-cho, Nishinomiya-shi, Hyogo -2-303 (72) Fujio Takahashi 1-1-13-207 Higashi-Naruo-cho, Nishinomiya-shi, Hyogo

Claims (1)

[Claims] 1. The following formula: (Wherein R ¹ is an alkyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group), and the following formula; [Wherein, X ¹ and X ² are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group represented by — (CH ₂ ) _z —OH (z is 1 to 3), and y is 0 to 2 A water-soluble lubricating rust preventive oil agent for plastic working, which comprises a salt with an amine represented by