JP2000109991A - Rust inhibitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a strong adsorption film on a metallic surface and to allow it to exhibit excellent corrosion preventive effect over a long period by allowing it to contain a compsn. contg. carboxylate with a specified molecular structure having plural carboxyl groups in the molecules or a reaction product between the aliphatic polycarboxylic acid and alkanolamine. SOLUTION: The carboxylate with a specified molecular structure having carboxyl groups to be used is the one with a structure of the formula I or II and, in the formulae, (m) is 0, 1 or 2, and R1-7 are respectively CnH2n+1 [(n) is 1 to 8]. As the alkanolamine, dimethylaminomethylpropanol, aminomethylpropanol, dimethylethanolamine or the like is given. The concn. of the rust preventive is desirably controlled to the range of 0.05 wt.% to the solubility, particularly of 0.1 to 15 wt.%. Various additives are added, e.g. a scale preventive is added to water or an organic solvent in which scale is easily precipitated, by which the generation of scale can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrophilic or lipophilic metal treatment agents, or is used as a metal working oil, or automotive coolants, hydraulic test chemical plants, such as LPG or LNG, or the like LNG tanker The present invention relates to a rust preventive agent which is added to and dissolved in water such as a cooling water for a water pressure test and an air conditioner, and is used for preventing corrosion of a metal constituting those devices.

[0002]

2. Description of the Related Art Conventionally, various rust preventives have been proposed and used, but they are low in toxicity, high in safety, easy to use, and have good stability. Few of them exhibit excellent rust prevention.

Many oil-soluble rust preventives such as petroleum allyl sulfonate are known. This is used for a long time as a rust preventive, but oil-soluble rust preventives have many problems in terms of flammability, work environment and resource saving, as well as automotive cooling and chemical plant. When used for various types of cooling, such as, for example, there is a problem that the cooling effect is poor. The solution was to emulsify and disperse oil-soluble ones.
So-called emulsion-type emulsions have been proposed and used, but not only do they cause adverse effects due to emulsifiers, but also it is difficult to ensure long-term stability, and they have not yet exhibited a sufficient rust-preventive effect. Therefore, a water-soluble rust inhibitor is regarded as important in order to solve these problems and to improve handling, safety and economy.

Conventionally, inorganic salts such as chromates, phosphates, and nitrites are known as water-soluble rust inhibitors. Chromates are highly toxic, and phosphates are wastewater. It causes eutrophication of rivers and seawater, and gives off bad odors to promote spoilage by microorganisms.

At present, it is said that a rust preventive made of a combination of a nitrite and a lower amine exhibits the most excellent rust preventive effect. Produces nitrosamines, which are recognized as substances, and poses a danger to the human body.

Therefore, recently, alkali metal salts of dibasic acids having 7 to 12 carbon atoms, such as disodium azelate, disodium sebacate or disodium decane-1,10-dicarboxylate, or C 7 to C 12 A rust preventive comprising an amine salt of dibasic acid such as triethanolamine or triethylenepentamine has been proposed and used.

[0007]

However, this rust preventive has a high melting point and is solid at room temperature. If a metal such as iron is subjected to a rust preventive treatment and stored, the rust preventive is accompanied by evaporation of water.
White crystals of the rust inhibitor precipitate and the adhesion to metal decreases,
As a result, rust easily occurs.

Further, this rust inhibitor is prohibited from being used by being added to automotive cooling water because of its suspicion of toxicity, and is used in other applications such as water-soluble cutting rust prevention applications. However, the rust-preventing effect is not satisfactory, and white crystals of the rust-preventive agent precipitate at the location where the cooling water leaks, not only impairing the appearance, but also causing rust to easily occur at the site. There are issues. For this reason, it is not satisfactory as compared with a rust preventive agent which combines a nitrite and a lower amine, which is conventionally determined to have the best rust preventive effect.

For this reason, recently, an alkali metal salt of a dibasic acid having 7 to 12 carbon atoms has been used as cooling water for automobiles. However, this does not provide a desired rust preventive effect. It is used by mixing phosphoric acid and phosphate with salt.

However, as described above, the use of phosphoric acid or phosphate causes eutrophication of rivers and seawater, and has a problem of deteriorating the natural environment, such as giving off odors to promote spoilage by microorganisms. .

Therefore, the present inventors have proposed the general formula [7] R ₁ OOC— (CH ₂ ) ₅ —R ₂ — (CH ₂ ) ₅ —COOR ₃ ... [7] where R ₁ and R ₃ are Na Or K, and R ₂ represents —CH ₂ —CH ＝ CH—CH ₂ ——CH ₂ —CH ＝ CH— (CH ₂ ) ₂ —CH ＝ CH—CH ₂
−,

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image Or

[0018]

Embedded image A water-soluble rust inhibitor containing a specific substance as an active ingredient has been proposed (JP-A-6-316780).

This water-soluble rust inhibitor uses a carboxylic acid salt having at least one carboxyl group in the molecule and having a specific molecular structure as a rust inhibitor, and is a liquid at room temperature. It is easy to embrace moisture, has high water retention, and has deliquescence.When a metal is treated with this rust inhibitor, it becomes liquid on the metal surface to form a uniform film, and the molecular chains are long and oriented. Because of its good property, it is easy to form a dense film on the metal surface. As a result, a strong adsorption film is formed on the metal surface, and an extremely excellent rust-preventing effect is exhibited over a long period of time.

However, rust preventives are often used as lipophilic metal surface treatment agents or metal working oils, but conventional rust preventives do not have satisfactory characteristics in such applications. Was.

The present invention has been completed in view of the above technical problem, and is one or more of carboxylic acid salts having a specific molecular structure and having a plurality of carboxyl groups in the molecule.
Or a reaction product of an aliphatic polycarboxylic acid having a specific structure and an alkanolamine.
When a seed or a composition containing two or more kinds is used as a rust preventive agent as an active ingredient, it is liquid at room temperature,
Or, it is easy to embrace moisture, has high water retention, and has deliquescence, so when a metal is treated with this rust inhibitor, it becomes liquid on the metal surface to form a uniform film, and the molecular chains are long and the orientation is high. It is easy to form a dense film on the metal surface because it is good, and a strong adsorption film is formed on the metal surface to exhibit an extremely excellent rust prevention effect over a long period of time. Rust preventives can be obtained from lipophilic to lipophilic ones, and the purpose of this lipophilic rust preventive is to provide a rust preventive suitable for use as a lipophilic metal surface treatment agent or metal working oil. And

[0022]

In order to solve the above-mentioned technical problems, the present inventors have been working for many years on one or two of alkali metal salts of organic acids having a plurality of carboxyl groups.
The relationship between the composition containing one or more species or the composition containing one or more of the reaction products of a specific aliphatic polycarboxylic acid and an alkanolamine and the rust preventive effect has been intensively studied.

As a result, a composition containing one or more of carboxylic acid salts having a specific molecular structure and having a plurality of carboxyl groups in the molecule, or an aliphatic polycarboxylic acid having a specific structure and an alkanolamine The rust preventive agent containing as an active ingredient a composition containing one or more of the above reaction products exhibits an extremely excellent rust preventive effect over a longer period than conventional water-soluble rust preventive agents. The rust inhibitor used in a wide range of applications from hydrophilic to lipophilic can be obtained by changing the molecular structure, and this specific lipophilic rust inhibitor is used as a lipophilic metal surface treatment agent. It has been found that when used as a metal working oil or a metal working oil, it has low toxicity as compared with conventional oil-soluble rust preventive agents, and exhibits stable and sufficient rust preventive effects over a long period of time. The present invention has been completed based on these findings.

That is, the rust inhibitor of claim 1 of the present application has the general formula
[1]

[0025]

Embedded image Or the general formula [2]

[0026]

Embedded image In the general formulas [1] and [2], m is 0, 1 or 2, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ or R ₇ is Na, K or a general formula, respectively. Equation [3]

[0027]

Embedded image And a composition containing one or more of the substances represented by the formula (1) as an active ingredient.

Further, the rust inhibitor of claim 2 of the present invention has the general formula [1]

[0029]

Embedded image Or the general formula [2]

[0030]

Embedded image In the general formulas [1] and [2], R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ or R ₇ is H or a general formula [3]

[0031]

Embedded image A composition containing one or more of the reaction products of an aliphatic polycarboxylic acid and an alkanolamine represented by the formula (1) as an active ingredient.

Further, the rust inhibitor of claim 3 of the present invention is the rust inhibitor according to claim 2, wherein the alkanolamine is at least one of dimethylaminomethylpropanol, aminomethylpropanol, dimethylethanolamine, aminoethylpropanediol and triethanolamine. It is something that is.

First, the rust inhibitor of claim 1 of the present application will be described in detail. In the present invention, in the substance having the basic structure represented by the general formula [1], particularly, m is 0, 1 or 2
And if R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ or R ₇ are each as described above, it is surprising that by treating the metal therewith, In addition, it is liquid at room temperature, or easily embraces moisture, has high water retention, and has deliquescence.As a result, it becomes liquid on the metal surface, and the metal surface is always in a wet state and a uniform film is formed. It is easy to form, has a long molecular chain, and has good orientation, so it forms a dense film on the metal surface and forms a strong adsorptive film on the metal surface to exhibit an excellent rust prevention effect over a long period of time. You do it.

In the present invention, by using such a substance as a rust inhibitor, low toxicity and high safety can be obtained.
It is easy to handle, has good stability, and is soluble in water, so there is no problem of fire or environmental destruction by dissolving it in water, it has a large cooling effect and is economical.
In addition, it exhibits extremely excellent rust-preventive power against various metals, particularly iron and aluminum, and furthermore, copper and zinc.

In the present invention, the above-mentioned specific substance may be used alone as a rust preventive, but may be used in combination of two or more kinds as a rust preventive. Depending on the kind of metal, two or more kinds may be used in combination. May be valid.

In this rust preventive, the alkali metal salt is easily dissolved in water, and is dissolved in water as it is, and is used as a water-soluble metal treating agent, cooling water for internal combustion engines of automobiles and trucks, water for heating / cooling, It is suitably used as water for hydraulic pressure testing of chemical plants such as LPG and LNG tankers, cooling water for air conditioning equipment, and liquid-cooled aircraft engines.

In the present invention, when dissolving the rust inhibitor in water or an organic solvent, the concentration of the rust inhibitor is 0.0.
It is desirable that the concentration is in the range of 5% by weight to the saturation concentration, particularly in the range of 0.1 to 15% by weight. If the concentration of the rust inhibitor is less than 0.05% by weight, the desired rust preventive effect may not be obtained. Yes,
On the other hand, if the concentration exceeds the saturation concentration, precipitation occurs in the apparatus, causing various adverse effects, which is not preferable.

In the present invention, a scale inhibitor is added to various additives used in the field of the rust preventive agent, for example, water or an organic solvent which easily precipitates scale.
It is possible to prevent the occurrence of scale. In this case, the compounding ratio of the additive may be a concentration higher than the effect of the additive is exerted and may be in a range that does not adversely affect the rust preventive effect, and is generally in the range of 0.1 to 1000 ppm. In using the metal rust preventive of the present invention, other known rust preventive components can be further used in combination.

The present invention is used as a rust inhibitor for metals such as iron, aluminum, steel and zinc and alloys thereof under a wide range of conditions.

Next, the rust preventive of claim 2 of the present invention will be described in detail. In the present invention, in the substance having the basic structure represented by the general formula [2], in particular, R ₁ , R ₂ , R ₃ , R ₄ , R
_If R ₅ , R ₆ or R ₇ are each as described above, then by treating the metal therewith, surprisingly, for the same reasons as in claim 1 of the present application, an excellent corrosion protection over a long period of time. The effect appears.

In the present invention, by using such a substance as a rust inhibitor, low toxicity and high safety can be obtained.
It is easy to handle, has good stability, and has fewer problems such as environmental destruction compared to conventional oil-soluble rust inhibitors.
It is economical, and among these types of rust preventives, water-soluble ones can be dissolved in water to avoid fires and environmental destruction, and have a large cooling effect and are economical. In addition, it exhibits an extremely excellent rust-preventive effect on various metals, particularly iron and aluminum, and copper or zinc.

In the present invention, the above-mentioned specific substance may be used alone as a rust preventive, but two or more kinds may be used as a rust preventive, and depending on the kind of metal, two or more kinds may be used in combination. May be valid.

This rust inhibitor is easily dissolved in water or an organic solvent due to the difference in its molecular structure, and is dissolved in water as it is, and is suitably used for the same applications as in the first aspect of the present invention.

In the present invention, when the rust inhibitor is dissolved in water or an organic solvent, the concentration of the rust inhibitor is 0.0.
It is desirable that the concentration is in the range of 5% by weight to the saturation concentration, particularly in the range of 0.1 to 15% by weight. If the concentration of the rust inhibitor is less than 0.05% by weight, the desired rust preventive effect may not be obtained. Yes,
On the other hand, if the concentration exceeds the saturation concentration, precipitation occurs in the apparatus, causing various adverse effects, which is not preferable.

In the present invention, a scale inhibitor is added to various additives used in the field of the rust preventive agent, for example, water or an organic solvent which easily precipitates scale.
It is possible to prevent the occurrence of scale. In this case, the compounding ratio of the additive may be a concentration higher than the effect of the additive is exerted and may be in a range that does not adversely affect the rust preventive effect, and is generally in the range of 0.1 to 1000 ppm. In using the metal rust inhibitor of the present invention,
In addition to the rust inhibitor of claim 2 of the present application, a known rust inhibitor component can be further used in combination.

The present invention is used as a rust inhibitor for metals such as iron, aluminum, steel and zinc and alloys thereof under a wide range of conditions.

Next, the rust preventive of claim 3 of the present invention will be described in detail. In the present invention, in the rust inhibitor of claim 2 of the present application, when the alkanolamine is at least one of dimethylaminomethylpropanol, aminomethylpropanol, dimethylethanolamine, aminoethylpropanediol or triethanolamine, It exhibits an extremely excellent rust prevention effect over a long period of time.

That is, in the present invention, by using such a substance as a rust preventive, the reaction product of the aliphatic polycarboxylic acid having the specific molecular structure with the alkanolamine forms a stable and harmful substance. As a result, it has low toxicity and high safety, is easy to handle, and has good stability, and has fewer problems such as environmental destruction compared to conventional oil-soluble rust preventives. It is economical, and among these types of rust preventives, water-soluble ones can be dissolved in water to use without causing problems such as fire or environmental destruction, and have a large cooling effect and are economical. In addition, it exhibits an extremely excellent rust-preventing effect on various metals, particularly iron and aluminum, and copper or zinc.

In the present invention, the reaction product of the above aliphatic polycarboxylic acid having a specific molecular structure and an alkanolamine may be used alone as a rust inhibitor.
A reaction product of two or more kinds of aliphatic polycarboxylic acids and one or more kinds of alkanolamines may be used as a rust inhibitor, and it is effective to use two or more kinds in combination depending on the kind of metal. There is.

In the present invention, the alkanolamine used is not particularly limited and may be used. Among them, dimethylaminomethylpropanol, aminomethylpropanol, dimethylethanolamine, aminoethylpropanediol or triethylamine At least one of ethanolamines is particularly desirable because of its good handleability, safety, long-term stability, rust prevention effect, economic efficiency, and the like.

This rust preventive is easily dissolved in water or an organic solvent, and is dissolved in water or an organic solvent as it is, and is suitably used for the same application as in the first aspect of the present invention.

In the present invention, when dissolving the rust inhibitor in water or an organic solvent, the concentration of the rust inhibitor is 0.0.
It is desirable that the concentration is in the range of 5% by weight to the saturation concentration, particularly in the range of 0.1 to 15% by weight. If the concentration of the rust inhibitor is less than 0.05% by weight, the desired rust preventive effect may not be obtained. Yes,
On the other hand, if the concentration exceeds the saturation concentration, precipitation occurs in the apparatus, causing various adverse effects, which is not preferable.

Further, in the present invention, a scale inhibitor is added to various additives used in the field of the rust preventive agent, for example, water or an organic solvent which easily precipitates scale.
It is possible to prevent the occurrence of scale. In this case, the compounding ratio of the additive may be a concentration higher than the effect of the additive is exerted and may be in a range that does not adversely affect the rust preventive effect, and is generally in the range of 0.1 to 1000 ppm. In using the rust preventive of the present invention, a known rust preventive component can be further used in combination with the rust preventive.

The present invention can be used as a rust inhibitor for metals such as iron, aluminum, steel and zinc and alloys thereof under a wide range of conditions.

[0055]

The rust inhibitor of claim 1 of the present application is a composition having the above structure and having one or more carboxylic acid salts having a specific molecular structure and having a plurality of carboxyl groups in the molecule. It is an active ingredient, which is liquid at room temperature, or has a high water-holding property because it easily embraces moisture, or has deliquescence. To form a uniform film,
Moreover, since the molecular chain is long and the orientation is good, it is easy to form a dense film on the metal surface, and a strong adsorption film is formed on the metal surface to exhibit an extremely excellent rust prevention effect over a long period of time. By changing the molecular structure, hydrophilic to lipophilic ones can be obtained, and this lipophilic rust inhibitor is suitable for use as a lipophilic metal surface treating agent or metal working oil. It has.

That is, one or two of carboxylic acid salts having a specific molecular structure and having a plurality of carboxyl groups in the molecule.
The composition containing more than one kind is a substance that easily becomes liquid or liquid.If this substance is dissolved in water or an organic solvent and the metal is treated with this solution, the metal surface will always be in a wet state. It is easy to form a uniform film, and since this film is dense and has a large amount of metal adsorption, it has an effect of exhibiting an extremely excellent rust prevention effect over a long period of time.

Further, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power as a single product, and has low toxicity, high safety and easy handling.
In addition, it has good stability, and water-soluble ones have no problem of fire or environmental destruction by dissolving in water, have a large cooling effect, are economical, and have various metals, especially It has the effect of exhibiting an extremely excellent rust-preventive effect on iron, aluminum, copper and zinc.

A rust preventive according to claim 2 of the present invention has a composition as described above and contains one or more reaction products of an aliphatic polycarboxylic acid having a specific structure and an alkanolamine. When used as a rust inhibitor containing an active ingredient as a rust preventive, this is liquid at room temperature, or it is easy to embrace moisture and has high water retention, and has deliquescence. It becomes a liquid on the surface and forms a uniform film.Moreover, the molecular chains are long and the orientation is good, so it is easy to form a dense film on the metal surface, and a strong adsorption film is formed on the metal surface. In addition to exhibiting excellent rust preventive action over a long period of time, it is possible to obtain from hydrophilic to lipophilic by changing the molecular structure, and this lipophilic rust inhibitor is lipophilic. Metal surface treatment agent and metal processing As it has a suitably activity used.

That is, a composition containing one or more of the reaction products of an aliphatic polycarboxylic acid having a specific structure and an alkanolamine has a property of being a liquid or a liquid easily. When a substance is dissolved in water or an organic solvent and the metal is treated with this solution, the surface of the metal is always wet and a uniform film is easily formed, and the film is dense and has a large adsorption to the metal. Therefore, it has an effect of expressing an extremely excellent rust prevention effect over a long period of time.

Also, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power as a single product, and is low in toxicity and high in safety, easy to handle and stable. It has good properties, and water-soluble ones dissolve in water, so there is no problem such as fire or environmental destruction.
It has a large cooling effect and is economical, and has an effect of exhibiting an extremely excellent rust-preventive effect on various metals, particularly iron and aluminum, and further copper or zinc.

The water-soluble rust inhibitor of claim 3 of the present application has the above-mentioned structure. In claim 2 of the present application, a specific alkanolamine is used.
It is liquid at room temperature or easily embraces moisture, has high water retention, and has deliquescence properties.If a metal is treated with this rust inhibitor, it becomes liquid on the metal surface and forms a uniform film. In addition, since the molecular chains are long and the orientation is good, it is easy to form a dense film on the metal surface. As a result, a strong adsorption film is formed on the metal surface to provide an extremely excellent protection for a long time. It exhibits a rust effect.

That is, a composition containing one or more of the reaction products of an aliphatic polycarboxylic acid having a specific structure and a specific alkanolamine has a property of easily becoming a liquid or a liquid. When this substance is dissolved in water or an organic solvent and the metal is treated with this solution, the surface of the metal is always wet and a uniform film is easily formed. In addition, this film is dense and adsorbs on the metal. Since it is large, it has an effect of exhibiting an extremely excellent rust prevention effect over a long period of time.

Further, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power by itself, and is low in toxicity and high in safety, easy to handle and stable. It has good properties, and water-soluble ones dissolve in water, so there is no problem such as fire or environmental destruction.
It has a large cooling effect and is economical, and has an effect of exhibiting an extremely excellent rust-preventive effect on various metals, particularly iron and aluminum, and further copper or zinc.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0065] A water-soluble rust inhibitor containing a substance represented by
Manufactured by the method.

That is, 500 g of 1,7-octanedicarboxylic acid (trade name: MMA-10, manufactured by Okamura Oil Co., Ltd.) and 1200 g of water were placed in a four-necked flask (a dropping port of an aqueous sodium hydroxide solution, a reflux condenser, a thermometer, After that, the temperature was raised to 80 to 100 ° C., and while maintaining the temperature, 414.2 g of a 47.8% by weight aqueous sodium hydroxide solution was added dropwise thereto. After the aqueous sodium hydroxide solution was added dropwise, the reaction was continued at 80 to 100 ° C. for about 1 hour, and then cooled to room temperature. Next, this aqueous solution was further diluted with water, and 2% of disodium 1,7-octanedicarboxylate was added.
A weight% aqueous solution was obtained. The acid value of the aqueous solution thus obtained was 0.06, and the pH was 9.41.

[0067] A water-soluble rust inhibitor containing a substance represented by
Manufactured by the method.

That is, 500 g of 7,8-dimethyl-7,8-dimethoxycarbonyl-1,14-tetradecanedicarboxylic acid (trade name: MMA-20, manufactured by Okamura Oil Co., Ltd.)
And 1100 g of water were mixed with 4 same as those used in Example 1.
After the flask was placed in a one-necked flask, the temperature was raised to 80 to 100 ° C., and 47.8% by weight was maintained therein while maintaining the temperature.
197.4 g of an aqueous sodium hydroxide solution is added dropwise. Approximately 1 hour after dropping the aqueous sodium hydroxide solution
After continuing the reaction at 0 ° C., it was cooled to room temperature. Then, this aqueous solution was further diluted with water to obtain 7,8-dimethyl-7,8.
A 2% by weight aqueous solution of dipotassium dimethoxycarbonyl-1,14-tetradecanedicarboxylate was obtained. The acid value of the aqueous solution thus obtained was 0.03, and the pH was 8.93.

[0069] A water-soluble rust inhibitor containing a substance represented by the following formula as an active ingredient was produced by the following method.

That is, 7,8-dimethyl-7,8-dimethoxycarbonyl-1,14-tetradecanedicarboxylic acid 24% by weight, 1,7-octanedicarboxylic acid 49% by weight, 7-methyl-7-methoxycarbonyl-1 14% by weight of 9,9-decanedicarboxylic acid, 7,9-dimethyl-7,
A dicarboxylic acid mixture composed of 13% by weight of 9-dimethoxycarbonyl-1,11-dodecanedicarboxylic acid (trade name: MMA-10R, manufactured by Okamura Oil Co., Ltd., neutralization value: 473.
1) After placing 500 g and 470 g of water in the same four-necked flask as used in Example 1, the temperature was raised to 80 to 1
The temperature was raised to 00 ° C, and while maintaining that temperature, 4
362.7 g of a 6.5% by weight aqueous sodium hydroxide solution are added dropwise. After the aqueous sodium hydroxide solution was added dropwise, the reaction was continued at 80 to 100 ° C. for about 1 hour, and then cooled to room temperature. Next, the aqueous solution of the sodium salt of the dicarboxylic acid mixture was further diluted with water to obtain a 2% by weight aqueous solution of the sodium salt of the dicarboxylic acid mixture. The acid value of the aqueous solution thus obtained was 0.12, and the pH was 8.73. In addition, Okamura Oil Co., Ltd. product name: MMA-10R
Since the components vary slightly depending on the lot, the amounts of sodium hydroxide, potassium hydroxide and the like are determined by the neutralization value.

[0071] A water-soluble rust inhibitor containing a substance represented by
Manufactured by the method.

That is, 360 g of triethanolamine was charged into a 3 liter glass beaker, and then water 5 was placed therein.
Add 60 g and dilute. After confirming that this solution was sufficiently mixed to form a uniform solution, 1,7-octanedicarboxylic acid (trade name: MMA-10, manufactured by Okamura Oil Co., Ltd.) 20
0 g is slowly added and stirred. The temperature of this solution can be up to 4
Raise to 6 ° C. The stirring was continued for about 2 hours, and the mixture was filtered with a filter paper having 6 μm of retained particles to remove impurities. Then
This aqueous solution was further diluted with water to obtain a 2% by weight aqueous solution of the above substance. The pH of the aqueous solution thus obtained was 8.21.

Example 5 A water-soluble rust inhibitor containing a substance produced by the following method as an active ingredient was obtained. That is, the same dicarboxylic acid mixture as used in Example 3 (trade name: MMA-10, manufactured by Okamura Oil Co., Ltd.)
R, provided that the neutralization number is 462.1) 500 g, 736 g of dimethylethanolamine and 1236 g of water are charged into a 5 liter glass beaker and mixed well to form a uniform solution. The temperature of the solution rises up to 42 ° C. The stirring was continued for 2 hours, and the particles were filtered through a filter paper having 6 μm of retained particles.
Contaminants were removed. Next, the reaction product of the dicarboxylic acid mixture and dimethylethanolamine was further diluted with water to obtain a 2% by weight aqueous solution of the reaction product. The pH of the aqueous solution thus obtained was 8.31. The aqueous solution of the reaction product of the dicarboxylic acid mixture and dimethylethanolamine before dilution with water had a solid content of 50% by weight according to a gravimetric method by drying.

[0074] An oil-soluble rust inhibitor containing a substance represented by the following formula as an active ingredient was produced by the following method.

That is, 7,8-dimethyl-7,8-dimethoxycarbonyl-1,14-tetradecanedicarboxylic acid (trade name: MMA-20, manufactured by Okamura Oil Co., Ltd.) 500
g, 1500 ml of methanol and 1.4 g of paratoluenesulfonic acid were placed in a four-necked flask similar to that used in Example 1, and then heated and refluxed at 60 to 70 ° C. for 3 hours to perform an esterification reaction. . After completion of the reaction, methanol is collected under reduced pressure, 500 ml of toluene is added, and washing with water is repeated until the pH of the washing solution becomes 6 to 7. After recovering the toluene under reduced pressure, the above substance is obtained. The yield of this material is 489
g, and its properties are pale yellow viscous liquid (room temperature)
Met. And the acid value of the above substance is 3.2,
Its saponification value was 251.0.

Example 7 A substance obtained by completely esterifying a dicarboxylic acid mixture similar to that used in Example 3 (trade name: MMA-10R, manufactured by Okamura Oil Co., Ltd., with a neutralization value of 462.1) Was obtained by manufacturing an oil-soluble rust preventive agent containing as an active ingredient the following method.

That is, MMA-10RM (Okamura Oil Co., Ltd.)
Product name: MMA-10R partially esterified product, acid value 51.3) 500 g, methanol 500 ml and p-toluenesulfonic acid 1.4 g were placed in a four-necked flask similar to that used in Example 1. Thereafter, esterification was performed completely in the same manner as in Example 6 to obtain an oil-soluble rust inhibitor. The yield of this substance was 456 g, and its properties were a flowable pale yellow liquid (room temperature). And the acid value of the said substance was 3.5, and the saponification value was 442.1.

Comparative Example 1 An aqueous solution of disodium azelate was used.

Comparative Example 2 An aqueous solution of dipotassium azelate was used.

Comparative Example 3 Azelaic acid and triethanolamine 1: 2 (molar ratio)
An aqueous solution of the mixture was used.

Comparative Example 4 An aqueous solution of disodium sebacate was used.

Comparative Example 5 An aqueous solution of dipotassium sebacate was used.

Comparative Example 6 An aqueous solution of a mixture of sebacic acid and dimethylethanolamine 1: 2 (molar ratio) was used.

Comparative Example 7 An aqueous solution of disodium dodecane diacid was used.

Comparative Example 8 An aqueous solution of dipotassium dodecane diacid was used.

Comparative Example 9 Dodecane diacid and triethanolamine 1: 2 (molar ratio)
An aqueous solution of the mixture was used.

Comparative Example 10 A complete ester compound of pentaerythritol and coconut oil fatty acid was used.

Reference Example 1

[0089]

Embedded image Was prepared by the following method.

That is, 450 g of 7.12-dimethyl-7,11-octadecadien-1,18-dicarboxylic acid (trade name: IPU-22, manufactured by Okamura Oil Co., Ltd.) and 450 g of water
g in a four-necked flask (with thermometer, sodium hydroxide aqueous solution dropping port, reflux condenser and stirrer).
The temperature was raised to １００100 ° C., and while maintaining the temperature, 216 g of a 47.7% by weight aqueous sodium hydroxide solution was dropped therein. The dripping time of this aqueous sodium hydroxide solution is 60
~ 65 minutes. After completion of the dropwise addition of the solution, the reaction was continued at a temperature of 90 to 95 ° C. for about 1 hour with further stirring.
Cooled to room temperature.

The solution thus obtained had an acid value of 0.09 and a pH of 9.32. This solution had a solid content of 23.7% by weight according to a gravimetric method by drying.

Rust prevention performance comparison test Rust generation test using steel sheet A rust generation test was performed by the following method. That is, first, Examples 6 and 7, Comparative Example 10, and Reference Example 1 were used, and each of these oil-soluble rust preventive agents was used as a naphthenic mineral oil [specific gravity (temperature of 15 ° C).
0.900, total acid value 0.05, flash point 150 ° C, pour point -50 ° C, viscosity (temperature 40 ° C) 9.2cSt] to 1 wt%, 5 wt% and 10 wt%, respectively. Thus, an oil-soluble rust inhibitor solution was obtained.

Next, two cold-rolled steel sheets (SPCC-SB) were
After polishing with No. 40 sandpaper, degreased with 1,1,1-trichloroethane was used.
Each of the cut pieces 1 was coated with the above oil-soluble rust preventive solution so as to have a concentration of 1 g / m ² .

Further, as shown in FIG. 1, the cut piece 1 obtained in this way was
Attached to a 50 mm rectangular through window 3, 90 to 9 hot water
Exposure for 1 hour in an atmosphere of steam S generated from 5 ° C.
As shown in FIG. 2, evaluation was made by the number of rusts after one hour. Table 1 shows the results.

[0095]

[Table 1]

Rust generation test using dry cutting chips of FC-20 casting About 10 g of chips were taken in a petri dish, and 0.1 g of the chip was placed in the petri dish.
02%, 0.1%, 1%, 2% and 3% by weight
The aqueous solutions of the rust preventives of Examples 1 to 5 and Comparative Examples 1 to 9 prepared as described above were added. Thus, the chips are immersed in the aqueous solution of each of the rust preventive agents for 10 minutes, filtered with 5 μm retaining particles, and the rust generation of the chips on the filter paper is observed over time. The results are shown in Tables 2 and 3, respectively.

[0097]

[Table 2]

[0098]

[Table 3]

The rust preventives of each of the examples and comparative examples were evaluated by the following 10-point evaluation method. 10-point evaluation method 72 hours later No rust 10 48-72 hours later 1-2 point rust 9 24-48 hours later 1-2 point rust 8 24 hours later 1-2 point rust 7 24 hours later Several points rust 6 12- After 24 hours Several rust 5 8 hours After several rust 4 6 hours After several rust 3 3 hours After several rust 2 1 hour After several rust 1

Rust generation test by immersion in steel sheet A cold rolled steel sheet (SPCC-SB) polished with # 240 sandpaper and degreased with 1,1,1-trichloroethane was used. This steel sheet (100 mm × 50 mm rectangle) was immersed for 10 minutes in the aqueous solutions of the rust preventives of Examples 4.5 and 5 and Comparative Examples 6.9 adjusted as shown in Tables 4 to 6, respectively. The state of rust generation 5 days after natural drying was observed. Table 4 shows the results.

[0101]

[Table 4]

Corrosion Test of Al Plate An Al plate (Al 1) was used instead of the cold-rolled steel plate (SPCC-SB).
050P / Japan Test Panel), and a rust prevention test was performed in the same manner as described above. Table 5 shows the results.

[0103]

[Table 5]

Copper Powder Corrosion Test Instead of dry cutting chips of FC-20 casting, 5 g of copper powder was taken in a petri dish and subjected to the same 10-point evaluation method test as described above. The results are shown in Tables 6 and 7, respectively.

[0105]

[Table 6]

[0106]

[Table 7]

From the test results shown in (1) to (4) above, it is recognized that those of the examples exhibit significantly superior rust preventive effects as compared with those of the comparative examples 1 to 10. In addition, it is recognized that the product of Reference Example 1 exhibits a relatively excellent rust prevention effect.

[0108]

According to the present invention, the water-soluble rust inhibitor of the present invention has one or more carboxylic acid salts having a specific molecular structure and a plurality of carboxyl groups in the molecule. The composition is an active ingredient, which is
It is liquid at room temperature, or easily embraces moisture, has high water retention, and has deliquescence, so it is liable to become liquid. It has a long molecular chain and good orientation, so it is easy to form a dense film on the metal surface. In addition to exhibiting effects, it is possible to obtain from hydrophilic to lipophilic by changing the molecular structure, and this lipophilic rust inhibitor is used as a lipophilic metal surface treatment agent or metal processing oil. As a result, an excellent effect is exhibited.

That is, one or two of carboxylic acid salts having a specific molecular structure and having a plurality of carboxyl groups in the molecule.
The composition containing more than one kind is a substance that easily becomes liquid or liquid.If this substance is dissolved in water or an organic solvent and the metal is treated with this solution, the metal surface will always be in a wet state. It is easy to form a uniform film, and since this film is dense and has high adsorption to metal, it exhibits an extremely excellent rust-preventive effect over a long period of time.

Further, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power as a single product, and has low toxicity, high safety and easy handling.
In addition, it has good stability, and water-soluble ones have no problem of fire or environmental destruction by dissolving in water, have a large cooling effect, are economical, and have various metals, especially It exhibits an extremely excellent rust-preventive effect on iron, aluminum, copper, and zinc.

The rust preventive according to claim 2 of the present invention has a composition as described above and contains one or more of the reaction products of an aliphatic polycarboxylic acid having a specific structure and an alkanolamine. When used as a rust inhibitor containing an active ingredient as a rust preventive, this is liquid at room temperature, or it is easy to embrace moisture and has high water retention, and has deliquescence. It becomes a liquid on the surface and forms a uniform film.Moreover, the molecular chains are long and the orientation is good, so it is easy to form a dense film on the metal surface, and a strong adsorption film is formed on the metal surface. In addition to exhibiting excellent rust preventive action over a long period of time, it is possible to obtain from hydrophilic to lipophilic by changing the molecular structure, and this lipophilic rust inhibitor is lipophilic. Metal surface treatment agent and metal processing Than it exhibits excellent effects as.

That is, a composition containing one or more reaction products of an aliphatic polycarboxylic acid having a specific structure and an alkanolamine has a property of easily becoming a liquid or a liquid. When a substance is dissolved in water or an organic solvent and the metal is treated with this solution, the surface of the metal is always wet and a uniform film is easily formed, and the film is dense and has a large adsorption to the metal. As a result, an extremely excellent rust prevention effect is exhibited over a long period of time.

Further, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power by itself, and is low in toxicity and high in safety, easy to handle and stable. It has good properties, and water-soluble ones dissolve in water, so there is no problem such as fire or environmental destruction.
It has a large cooling effect and is economical, and exhibits an extremely excellent rust-preventive effect against various metals, especially iron and aluminum, as well as copper and zinc.

The water-soluble rust inhibitor of claim 3 of the present application has the above-mentioned structure. In claim 2 of the present application, a specific alkanolamine is used.
It is liquid at room temperature or easily embraces moisture, has high water retention, and has deliquescence properties.If a metal is treated with this rust inhibitor, it becomes liquid on the metal surface and forms a uniform film. In addition, since the molecular chains are long and the orientation is good, it is easy to form a dense film on the metal surface. As a result, a strong adsorption film is formed on the metal surface to provide an extremely excellent protection for a long time. It exhibits the rust effect.

That is, a composition containing one or more of the reaction products of an aliphatic polycarboxylic acid having a specific structure and a specific alkanolamine has a property of easily becoming a liquid or a liquid. When this substance is dissolved in water or an organic solvent and the metal is treated with this solution, the surface of the metal is always wet and a uniform film is easily formed. In addition, this film is dense and adsorbs on the metal. Since it is large, it exhibits an extremely excellent rust prevention effect over a long period of time.

Further, in the present invention, by using such a substance as a rust preventive, it exhibits excellent rust preventive power as a single product, and is low in toxicity, high in safety, easy to handle and stable. It has good properties, and water-soluble ones dissolve in water, so there is no problem such as fire or environmental destruction.
It has a large cooling effect and is economical, and exhibits an extremely excellent rust-preventive effect against various metals, especially iron and aluminum, as well as copper and zinc.

[Brief description of the drawings]

FIG. 1 is a perspective view specifically showing a method of an evaluation test of each rust preventive agent.

FIG. 2 is a perspective view specifically showing the state of rust generation.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cut piece 2 FRP board 3 Penetration window S Steam

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Yoshida Kida, Inventor 4-5 Kawaramachi, Kashiwara-shi, Osaka F-term in Okamura Oil Co., Ltd. (Reference) 4H025 AA17 AA35 4K062 AA03 BB06 BB15 FA05 GA08

Claims (3)

[Claims] 1. A compound of the general formula [1] Or the general formula [2] In the general formulas [1] and [2], m is 0, 1 or 2, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ or R ₇ is Na, K or a general formula, respectively. Formula [3] A rust preventive comprising as an active ingredient a composition containing one or more of the substances represented by 2. A compound of the general formula [1] Or the general formula [2] In the general formulas [1] and [2], R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R _{6 and} R ₇ are each H or a general formula [3] A rust inhibitor comprising, as an active ingredient, a composition containing one or more of the reaction products of an aliphatic polycarboxylic acid and an alkanolamine represented by the formula: 3. The rust inhibitor according to claim 2, wherein the alkanolamine is at least one of dimethylaminomethylpropanol, aminomethylpropanol, dimethylethanolamine, aminoethylpropanediol and triethanolamine.