JPH0762568A - Water-in-oil type rust inhibitor - Google Patents

Abstract

PURPOSE:To provide a water-in-oil type rust inhibitor which is uninflammable, enhanced in safety and capable of excellently preventing the rusting and spotting of metal by a corrosive acidic gas over a long period. CONSTITUTION:A sulfonate (1-30 pts.wt.), a sorbitan ester of fatty acid (1-30 pts.wt.) and oxidized wax (2-30 pts.wt.) are mixed in a petroleum base oil (15-65 pts.wt.), dispersed and/or dissolved, then water (5-70 pts.wt.) is added in small amts. by using a homomixer, a specified amt. of water is added, then the addition of water is continued for a specified time, and a water-in-oil type rust inhibitor is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil type rust preventive which exhibits no flammability, no risk of fire occurrence, and excellent rust preventive performance maintained for a long period of time.

[0002]

2. Description of the Related Art Iron and other metals are susceptible to corrosive acid gases containing moisture and sulfur oxides, nitrogen oxides, etc. in the air, and corrosion such as rust, stains or pitting corrosion on the metal surface. If it occurs, the quality and quality of metal products will be impaired. Therefore, more rust preventive agents have been used than before for the purpose of preventing corrosion of metal products. As the rust preventive agent, an oil-soluble rust preventive agent such as a solvent-diluted rust preventive oil or a lubricating oil type rust preventive oil, an oil-soluble rust preventive agent, as defined in Japanese Industrial Standard (JIS) K2246 (rust preventive oil) An oil-in-water type rust inhibitor in which a rust agent is emulsified or dispersed in water with a small amount of a surfactant, and a water-soluble rust inhibitor such as a transparent soluble rust inhibitor mainly composed of a water-soluble organic or inorganic rust inhibitor. Anti-corrosion agents are known. These rust preventive agents are used properly such as an oil-soluble rust preventive agent for a metal product which requires rust preventive over a long period of time, and a water soluble rust preventive agent for a short term.

However, in the above oil-soluble rust preventive agent,
There is a risk of fire during storage or use, and there is a problem that it is uneconomical because it requires a lot of cost for facilities and equipment to prevent it and ensure safety. For rust prevention of metal parts,
The above-mentioned problems in terms of both safety and economy become more serious, for example, the storage tank for the rust preventive agent has a large capacity. On the other hand, a water-soluble rust preventive does not have a safety problem such as a fire like an oil-soluble rust preventer, but protects a metal from corrosive acid gas containing moisture in the air, sulfur oxides, etc. The performance is not sufficient, and rusts on the metal surface in a relatively short time,
There is a problem that corrosion such as stains and pitting occurs.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems and is highly safe and particularly prevents corrosion of metal such as rust and stains due to corrosive acid gas for a long period of time. It is an object to provide a rust preventive agent that can

[0005]

Means for Solving the Problems As a result of diligent studies on the components of a rust preventive agent, the influence of corrosive acid gas, etc., the present inventors have shown that the composition does not exhibit flammability and has excellent rust preventive performance and an emulsion / dispersion. They found a method and completed the present invention.
That is, the water-in-oil type rust preventive agent of the first aspect of the present invention disperses and / or dissolves (A) sulfonate, (B) sorbitan fatty acid ester, and (C) salt of oxidized wax in (D) petroleum-based base oil. It is characterized by containing the mixture thus obtained and (E) water. Furthermore, the water-in-oil type rust preventive agent of the second aspect of the present invention has 1 to 30 parts by weight of (A) sulfonate and 1 to 30 parts of (B) sorbitan fatty acid ester when the total amount of rust preventive agent is 100 parts by weight. Parts by weight, 2 to 30 parts by weight of (C) oxidized wax, 15 to 65 parts by weight of (D) petroleum base oil, and (E)
The water is 5 to 70 parts by weight.

The above-mentioned "(A) sulfonate" [hereinafter referred to as the component (A)] strongly adsorbs itself to the metal surface and suppresses the reaction between metal atoms and water and oxygen, and exhibits a rust preventive effect. It is a component of synthetic or petroleum sulfonate.
One kind or two or more kinds can be used. The synthetic sulfonate, obtained in petrochemical, other than those obtained by sulfonation of alkylnaphthalene such as alkylbenzene or dinonylnaphthalene, dialkylsulfosuccinic acid ester salt, alkylsulfoacetic acid salt,
Examples include α-olefin sulfonate. Also,
The petroleum sulfonate is obtained by neutralizing a sulfonic acid mixture of hydrocarbons, which is a by-product when a petroleum fraction is purified with sulfuric acid, with an alkali component. The content of the component (A) is, when the total amount of the rust preventive agent is 100 parts by weight (hereinafter, the compounding amount of each component is the same).
A range of 1 to 30 parts by weight is preferable. When the content is less than 1 part by weight, the rust preventive property is insufficient, and when it exceeds 30 part by weight, the liquid stability of the rust preventive agent is lowered and the oil content is floated to exhibit flammability, which is not preferable.

The above "(B) sorbitan fatty acid ester"
[Hereinafter, referred to as component (B)] has the effect of supplementing the rust preventive performance of component (A) and improving the liquid stability. As the component (B), mono-, di-, and triesters of sorbitan and higher fatty acids such as lauric acid, palmitic acid, stearic acid, and oleic acid can be used. The content of the component (B) is preferably in the range of 1 to 30 parts by weight. When the content is less than 1 part by weight, the stability of the liquid is lowered, and when it exceeds 30 parts by weight, the content of unreacted hydroxyl groups is increased and moisture absorption rather reduces the rust preventive property, which is not preferable.
Further, in the present invention, other than the above-mentioned component (B), other fatty acid ester, for example, glycerin fatty acid ester, propylene glycol fatty acid ester and the like may be used in suitable amounts.

The above-mentioned "(C) Salt of oxidized wax"
The component (C) is effective in maintaining the liquid stability of the rust preventive agent, preventing the corrosive acid gas from entering, and suppressing the generation of stains. As the component (C), an alkali salt of an oxide of petroleum wax such as paraffin wax, microcrystalline wax and petrolatum having an acid group, and an alkali salt of an oxide of polyethylene wax, atactic polypropylene wax and the like having an acid group. Salt or the like can be used. Examples of the alkali include alkanolamines such as alkylamine, ethanolamine and diisopropanolamine, alkali hydroxides such as sodium hydroxide and potassium hydroxide, ammonia and morpholine. The acid value of the oxidized wax constituting the component (C) is suitably in the range of 20-80. When the acid value is less than 20, the liquid stability is lowered, and when the acid value exceeds 80, rust is easily generated due to moisture absorption, which is not preferable.
Further, the content of the component (C) is preferably in the range of 2 to 30 parts by weight. When the content is less than 2 parts by weight, the liquid stability is lowered, and when it exceeds 30 parts by weight, the composition containing the components (A), (B) and (C) has the above-mentioned “(D) petroleum base oil”. Is difficult to disperse and / or dissolve, and the liquid stability decreases, which is not preferable.

The "(D) petroleum-based base oil" in which the compound containing the above-mentioned components (A), (B) and (C) is dispersed or dissolved is a mineral oil, a petroleum-based solvent such as machine oil or turbine oil. , Spindle oil, light oil, kerosene, petrolatum, etc. can be used alone or in combination. The content of component (D) is preferably in the range of 15 to 65 parts by weight. Content is 1
If it is less than 5 parts by weight, the above components (A), (B) and (C)
Is not sufficiently dissolved and / or dispersed, and when it exceeds 65 parts by weight, the contents of other components are relatively small, and the liquid stability and the rust preventive property are deteriorated, which is not preferable. Further, the content of "(E) water" used in the present invention is preferably in the range of 5 to 70 parts by weight. If the content is less than 5 parts by weight, the resulting rust preventive agent becomes flammable, and
This is because if it exceeds 0 parts by weight, it will not be a water-in-oil type rust preventive agent. The water-in-oil type rust preventive agent of the present invention is composed of the above essential components, but as other optional components, as additives conventionally used in rust preventive agents, for example, antioxidants, non-ferrous metal anticorrosion agents. Additives such as agents, thickeners, preservatives and dispersants can be appropriately mixed and used.

[0010]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. (1) Preparation of rust preventive agent Components (A), (B) and (C) of each rust preventive agent of Examples 1 to 11 were mixed, and this mixture was mixed with component (D) to disperse or dissolve. After that, 600 rpm using a homomixer
While stirring at 0 rpm, add the component (E) little by little,
After adding a predetermined amount of component (E), stirring was continued for further 20 minutes to obtain a water-in-oil type rust preventive agent. All the obtained rust preventives were stable even after standing at 40 ° C. for 2 weeks without any liquid separation. Table 1 shows the composition of the rust preventive agent of each example. still,
The numerical values showing the composition in Table 1 represent parts by weight.

[0011]

[Table 1]

(2) Each component in Table 1 Sulfonate a) King Company, trade name "Nassle BSN" (barium salt) b) Witco Co., trade name "Sirchem 404" (barium salt) c) Matsumura Petroleum Research Co., Ltd. "Sulhol CA45N" (calcium salt) d) Witco, trade name "calcium petronate"
(Calcium salt) e) Made by Matsumura Oil Research Institute, product name "Sulhol 465"
(Sodium salt) sorbitan fatty acid ester a) sorbitan monolaurate b) sorbitan monostearate c) sorbitan sesquioleate d) sorbitan trioleate e) sucrose fatty acid ester

Oxidized wax salt a) Triethanolamine salt of ALOX 600, trade name “ALOX600” (petrolatum oxide, acid value; 60) b) Nippon Seiwa Co., Ltd., trade name “OX0450” (oxidized petrolatum, acid Value; 37) cyclohexyldiethanolamine salt c) Nippon Seiro Co., Ltd., trade name "NPS9035" (oxidized microcrystalline wax, acid value; 47) ammonium salt d) Nippon Seiro Co., Ltd., trade name "NPS3185" (oxidation Paraffin wax, acid number; 30) triethylamine salt petroleum-based base oil a) No. 68 turbine oil b) Nippon Oil Co., Ltd., trade name "Neutral Oil 30" c) Nippon Oil Co., Ltd., trade name "RC Spindle Oil" d ) Nippon Oil Co., Ltd., trade name "insecticide solvent" e) White kerosene

(3) Performance Test In order to clarify the performance of the water-in-oil type rust preventive agent of the present invention, performance evaluation of flammability, rust prevention and oil stain resistance was performed by the following methods. Flammability The flash point was measured by the flash point measurement test method for dangerous goods class 4 specified by the Fire Service Law. In addition, in the display of evaluation, a numerical value indicates a flash point (° C.) and a − indicates that the flash point was not shown. Rust prevention and oil stain resistance The rust resistance and oil stain after 30 days were examined according to the storage and storage test method specified in Japanese Industrial Standard (JIS) K2246 (rust preventive oil). In addition, the display of rust prevention evaluation is
◎: No rust, ○: 1-10% surface rust, △: 11-25
% Surface rust, ×; 26 to 50% surface rust, XX; 51% or more represents surface rust generation, and the indication of oil stain resistance evaluation is ⊚: no oil stain, ×: oil stain generation. The results are shown in Table 2.

[0015]

[Table 2]

As Comparative Example 1, a solvent-diluted rust preventive (manufactured by Yushiro Chemical Co., Ltd., trade name "Non-Raster P") was used.
313 "), and as Comparative Example 2, a lubricating oil type rust preventive (manufactured by Yushiro Chemical Co., Ltd., trade name" Non-Raster P93 ").
1 ”), and as Comparative Example 3, oil-in-water type rust preventive (manufactured by Yushiro Chemical Co., Ltd., trade name“ Non-Raster PSW ”).
2 ”), and as Comparative Example 4, a transparent soluble rust preventive agent (manufactured by Yushiro Chemical Co., Ltd., trade name“ Non-Raster W ”).
6 ") was diluted with 5 times water.

According to the results of Table 2, the component (A),
Regardless of the blending amounts of (B), (C), (D) and (E), the rust preventives of any of the examples showed no flammability, and both rust and oil stains were generated. I know that not. On the other hand, the rust preventives of Comparative Examples 1 and 2 are flammable, the rust preventive of Comparative Example 3 is poor in both rust preventive property and oil stain resistance, and the rust preventive of Comparative Example 4 is very poor. Therefore, it can be seen that none of the anticorrosive agents of each comparative example has good flammability, antirust property, and oil stain resistance. The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application.

[0018]

INDUSTRIAL APPLICABILITY The water-in-oil type rust preventive agent of the present invention does not show flammability like the conventional water-soluble rust preventive agent, and there is no danger of fire or the like. In addition, rust resistance and oil stain resistance are as good as those of conventional oil-soluble rust inhibitors.

Claims (2)

[Claims] 1. A salt of (A) sulfonate, (B) sorbitan fatty acid ester, and (C) oxidized wax is added to (D).
A mixture obtained by dispersing and / or dissolving in a petroleum base oil,
(E) A water-in-oil type rust preventive containing water. 2. When the total amount of the rust preventive agent is 100 parts by weight, the (A) sulfonate is 1 to 30 parts by weight, the (B) sorbitan fatty acid ester is 1 to 30 parts by weight, and the (C) oxidation is performed. 2 to 30 parts by weight of wax salt, 15 to 65 parts by weight of (D) petroleum base oil, and (E)
The water-in-oil type rust preventive agent according to claim 1, wherein the amount of water is 5 to 70 parts by weight.