KR100365708B1 - DETERGENT COMPOSlTION COMPRISING ANTIOXIDANT - Google Patents

Abstract

Cleaner composition characterized in that at least one selected from the group consisting of diisopropylamine, dicyclohexylamine, 1-methyl-2-pyrrolidone and 2-ethoxyethanol is 0.1% to 5% in a chlorine-based cleaner It starts.

Description

Detergent composition with antioxidant added {DETERGENT COMPOSlTION COMPRISING ANTIOXIDANT}

The present invention relates to an antioxidant for chlorine-based cleaners. More specifically, when washing the contaminated material with a chlorine solvent based cleaning agent in the manufacture of metal products, chlorine-based to prevent the corrosion and oxidation of metal products caused by various causes, or at least to minimize these corrosion or oxidation It relates to antioxidant for cleaning agent.

This red hair, which is one of the applicants, has applied for a chlorine-based detergent composition that does not contain 1,1,1-trichloroethane, which has an adverse effect on the ozone layer, and has been patented (see Patent No. 109092).

The patent is a cleaning composition composed of methylene chloride, solvents of chlorine compounds, alkanes, esters, ketones, and alcohols, without using a compound that adversely affects the ozone layer. When the composition is left for a long time, oxidation of the cleaning composition occurs, and when the object to be cleaned is a metal, there is a drawback of oxidative corrosion of the metal product.

In order to solve this problem, the inventors first considered adding an antioxidant to the cleaning agent. However, until now most cleaners have hardly recognized the need to add antioxidants as surfactants and industrial cleaners.

Accordingly, the present inventors conducted various studies in order to search for the antioxidant for the above chlorine-based cleaner, and as a result, it is preferable that the organic base is organic basic because there is a high risk of oxidizing a metal or the like when the antioxidant is acidic. Heavy primary amines and the like are not preferable because they easily react. Also, when an antioxidant is added to the cleaning agent, if the density is large, compatibility is poor, or even if phase separation does not occur, it is not uniform even in the same phase. It is preferable that the density does not increase even when added, and when the viscosity is increased when the antioxidant is added to the cleaning agent, it is found that there is a problem such as that the cleaning agent cannot be sprayed, and various organic compounds are used as the antioxidant. As a result of examination using dialkylamines, Ami The present invention has been completed by discovering that one or two or more selected from the group consisting of Drews and alkoxyalcohols can effectively function as antioxidants.

1 to 7 show an enlarged image of 500 times with an electron scanning microscope of the results of Example 1, FIG. 1 shows a blank, FIG. 2 shows an untreated detergent base, and FIG. 3 shows a treatment with a detergent base. 4 shows treatment with a solution in which 1-methyl-2-pyrrolidone 1% (V / V) was added to the detergent base, and FIG. 5 shows 1% of 2-ethoxyethanol (V / in the detergent base). The result of processing with the liquid which added V) is shown, FIG. 6 shows the result of processing with the liquid which added 1% (V / V) of diisopropylamine to the detergent base, and FIG. 7 shows dicyclohexyl in a detergent base. The result of processing with the liquid which added 1% of amine (V / V) is shown.

Antioxidant is added to the mixed detergent of the chlorine-based organic solvent to maintain the pH range of the detergent to 8-11, thereby chemically buffering the oxidation of the metal, and additives suppress chemical reaction with the constituent solvent of the mixed detergent, As a result of the examination of a compound which does not raise the viscosity and does not increase the viscosity, dialkylamines such as diisopropylamine and dicyclohexylamine and amides such as 1-methyl-2-pyrrolidone and 2-e Alkoxy alcohols, such as oxyethanol, are mentioned, Even if 1 type (s) or 2 or more types of these are added, there exists an outstanding antioxidant effect.

First, the physical properties of the compounds used in the present invention are shown in Table 1 below.

When cleaning products contaminated with copper, food, mineral oil or other organic compounds such as insulating grinding oil which is adsorbed during the processing of metal products with chlorine solvent, the surface of the object is gradually oxidized over time. In order to secure this problem, oxidative corrosion was significantly reduced than before administration by selecting and administering an additive capable of chemically buffering. In order to adjust the ratio of effective additives, physical properties, and field application, the additives were mixed with the chlorine-based cleaning agent and the following items were tested.

1. Preparation of detergent

First, a detergent without addition of an antioxidant was prepared according to Example 1 of Patent No. 109092.

That is, 3 l of acetone, 2 l of isopropyl alcohol, 1 l of butanol, 1 l of ethanol, 50 ml of polyoxyethylene octylphenol ether (HLB: 13.6, manufactured by Korea Polyol Co., Ltd.) and 300 ml of limonene, which are hydrophilic surfactants, were sufficiently stirred, Prepare A solution.

In addition, 47.5 L of methylene chloride, 28.5 L of trichloroethylene, 6.5 L of tetrachloroethylene, and 140 ml of polyoxyethylene octylphenol ether (HLB: 8.1, manufactured by Korea Polyol Co., Ltd.), which are lipophilic surfactants, were mixed. Stir enough to prepare liquid B.

On the other hand, 7 L of pentane which is a non-chlorine compound, 3 L of methyl acetate, and 10 ml of polyoxyethylene octyl phenol ether (HLB: 8,1, made by Korea Polyol Co., Ltd.) which are lipophilic surfactants are mixed and stirred, and C liquid is prepared.

82.84 L of the chlorine-based mixture of the liquid B and 7.35 L of the liquid A were mixed with stirring (360 rpm) at 30 ° C. for 5 hours to prepare a liquid D.

10.01 L of the C solution and 89.99 L of the D solution were mixed under stirring at 30 ° C. to obtain a composition containing no antioxidant.

Silica gel and alumina gel were added to the composition obtained as described above, l20 g each, aged at 360 rpm for 5 hours to remove moisture and odor in the composition, and then filtered and used as a detergent base in the present invention.

2. Hydrogen ion concentration (PH) measurement

Diisopropylamine, dicyclohexylamine, 1-methyl-2-pyrrolidone and 2-ethoxyethanol in the ratio of 1 to 10% were respectively added to the detergent base to confirm chemical buffering action for the oxidation of metal. Add. 5 ml of the added sample is collected, diluted with 10 ml of water, and mixed vigorously. After allowing the aqueous layer and the organic layer to separate, the electrode was fixed to the aqueous layer and pH was measured using Orion 960 (trade name). The results are shown in Table 2 below.

As shown in Table 2, when 1 to 10% of 1-methyl-2-pyrrolidone was added, the pH was 8.41 to 8.82, and it was found to increase gradually. In the case of 2-ethoxyethanol, the pH tends to decrease from 7.62 to 7.32 as the composition percent of the additive increases from 1 to 7%, and then increases again from 9% or more. Diisopropylamine and dicyclohexylamine have been observed to gradually increase their pH in the range of 12.20 to 12.79 and 10.83 to 11.48, respectively, at a content of 1-10%. You can see that.

3. Density measurement

Pyconometer by Micromertitcs (model: Accupyc 1330, USA) was prepared by adding diisopropylamine, dicyclohexylamine, 1-methyl-2-pyrrolidone, and 2-ethoxyethanol at a ratio of 1 to 9% to the detergent base, respectively. ) Was measured at room temperature (25 ° C). The density of the detergent without additives was 1.310∼1.320, and as the concentration of the additive was increased, it could be seen that it gradually decreased in the range of 1.305∼1.233. This is shown in Table 3 below.

4. Viscosity Measurement

When cleaning the metal products by the spray method, etc., the cleaning agent to be used must match the existing equipment, and the viscosity of the detergent mixed with the additive was measured. A sample in which diisopropylamine, dicyclohexylamine, 1-methyl-2-pyrrolidone, and 2-ethoxyethanol was added at a ratio of 1 to 9% to the detergent base was respectively cooled to room temperature using an Osstwald's viscometer. Measured at 25 ℃) and the viscosity coefficient (viscosity) ) Was obtained. The viscosity of the sample had a viscosity of about 0.45 to 0.55, and the viscosity increases as the amount of the additive was increased. It can be seen that as the concentration increases due to the viscosity of the additive, it becomes relatively large. This is shown in Table 4.

From the above results, the amount of the antioxidant additive added to the detergent base is considered to be the extent to which the antioxidant power can be maintained, the economical efficiency, the maintenance of the cleaning power of the detergent, and the residue of the detergent component remains in the to-be-washed material and foreign matters are considered. Diisopropylamine can maintain a high pH with a small amount (0.1-0.3% (v / v)) of administration and has antioxidant properties. In addition, dicyclohexylamine may have antioxidant power even with a small amount of administration, such as diisopropylamine. However, when it is administered in an excessive amount, dicyclohexylamine may act as an impurity in the process of metal processing. Can be. 1-Methyl-2-pyrrolidone and 2-ethoxyethanol can be seen only when an excessive amount is administered compared to dialkylamine. However, since 1-methyl-2-pyrrolidone and 2-ethoxyethanol have an excellent cleaning effect on their own, the amount of 1-methyl-2-pyrrolidone and 2-ethoxyethanol is increased to improve the cleaning power It can be increased up to 5%.

Therefore, the amount of the additive to be administered for the reasons listed above is preferably 0.1 to 5% with respect to the detergent base in an amount for maintaining the antioxidant power. Less than 0.1% is hardly anti-oxidation effect, and more than 5% is economically lost because the effect of excess does not increase.

Example 1

In order to check the antioxidant power of the above-mentioned additives, cut the iron plate (material SS400) specimens having the same conditions in the detergent base without additives and the additive dose detergent, wash the surface with acetone, and dry for 20 minutes. Thereafter, the resultant was volatilized, and the cleaning agent was volatilized, immersed in 4% saline for 24 hours to be oxidized and corroded, and then photographed at 500 × using an electron scanning microscope (SEM: Topcon ABT-32 / 5, JAPAN). 1 (blank), FIG. 2 (non-cleaner base treatment), FIG. 3 (cleaner base treatment), FIG. 4 (treatment with 1-methyl-2-pyrrolidone 1% (V / V) additive to the detergent base), FIG. 5 (treated with 1% (V / V) addition of 2-ethoxyethanol to the detergent base), FIG. 6 (treated with 1% (V / V) addition of the diisopropylamine to the detergent base), FIG. Treated with a dicyclohexylamine 1% (V / V) addition solution to the base).

By combining a small amount of the antioxidant of the present invention with a chlorine-based cleaner, when the contaminated material is washed with a chlorine-based cleaner, the corrosion and oxidation of the metal product caused by various causes is prevented.

Claims (1)

At least one cleaning agent selected from the group consisting of diisopropylamine, dicyclohexylamine, 1-methyl-2-pyrrolidone and 2-ethoxyethanol is blended at 0.1 to 5 wt% with respect to the chlorine-based cleaner, The pH is 8-11, and the density | concentration is the cleaning composition characterized by the range of 1.233-1.305 at 25 degreeC.