JPS6014108B2 - anti-rust - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel rust preventive agent that has excellent rust preventive properties and low foaming properties.

Traditionally, rust preventives have been made using inorganic compounds such as chromates, phosphates, and sodium nitrite, as well as alkylamines, alkylpolyamines, condensates of fatty acids and polyalkylesopolyamines, and alkylene oxides and amines. Organic compounds such as adducts are mainly used.

Of these, inorganic ones generally have poor lubricity, chromium-based ones are toxic, phosphorus-based ones cause eutrophication of wastewater, and nitrite-based ones turn into carcinogenic nitrosamines. Their use has begun to be regulated due to pollution problems, and the use of organic materials is gradually shifting to organic ones.

However, the rust preventive effect of currently used organic rust preventive agents is still not sufficient, and inorganic compounds such as sodium nitrite are mainly used. However, each of the above-mentioned inorganic rust preventive agents alone does not have a sufficient rust preventive effect, and the current situation is to use a mixture of various organic and inorganic compounds depending on the purpose. In addition, when conventional organic rust preventive agents are used as water-soluble rust preventive agents, they foam violently, resulting in insufficient rust preventive effects and poor operability. There has been a strong desire for the emergence of an excellent organic rust preventive agent. As a result of intensive research to solve the above problems, the inventors of the present invention have developed a low-foaming organic inhibitor that exhibits an excellent rust-preventing effect even when used in small amounts and without being mixed with other inorganic compounds. Developed a rust agent.

That is, the rust preventive agent of the present invention is a rust preventive agent containing an alkali salt of carboxylic acids represented by the general formula [1] as an essential component.

In formula [1], R,,R2 are alkylene groups having 1 to 6 carbon atoms, and X is S02 group or alkylene group having 1 to 5 carbon atoms (
may have a lower alkyl side chain having 4 or less carbon atoms), R
3, R4 represents an alkyl group having 1 to 4 carbon atoms, and m and n each represent 0 or an integer of 1 to 3. The carboxylic acids used in the present invention include bis(4-oxyphenyl)sulfon-○,0-dialkylcarboxylic acids such as bis(4-oxyphenyl)sulfon-○,0-diacetic acid, bis(4-oxyphenyl)sulfon-○,0-diacetic acid,
4-oxyphenyl)sulfone-○,0-dipropionic acid, etc., bis(4-oxyphenyl)alkane-○,
0-dialkylcarboxylic acids such as bis(4-oxyphenyl)methane-○,0-diacetic acid, B,8-pis(4-
oxyphenyl)propane-○,0-diacetic acid, 3,6-bis(4-oxyphenyl)propane-1○,0-dipropionic acid, bis(4-oxyphenyl)methane-○,0
- dibutyric acid etc.

Furthermore, 2,2'-methylenebis(4-ethyl-6-tert-butylphenoxyacetic acid) and 2,2'-methylenebis(4-methyl-6-tert-butylphenoxypropionic acid) can also be used. These carboxylic acids can be easily synthesized from a phenol compound and a halogenated carboxylic acid by a known method.

(For example, Special Publication No. 29-1834, J. AppIChe
m. Vol 9, 594, 1959). Next, examples of the alkali that can be used in the present invention include caustic soda, caustic potash,
Salts of alkali metals and alkali metals such as sodium phosphate, sodium carbonate, potassium phosphate, and calcium hydroxide: ammonium salts; methylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine, and salts of alkaline metals such as sodium phosphate, sodium carbonate, potassium phosphate, and calcium hydroxide; These include lower amines such as hexylamine.
In order to produce an alkali salt of carboxylic acids, both may be mixed and heated if necessary.

At this time, an organic solvent or water that dissolves both components, or a mixture of both may be used as the reaction solvent. The mixing ratio of carboxylic acids and alkali may be equivalent or one may be in excess, but in general, an excess of alkali is preferable from the viewpoint of solubility in water. The rust preventive agent of the present invention is not particularly limited in its usage, and as with conventional rust preventive agents, water,
Used by dissolving in oil or emulsion liquid.

However, those that are difficult to dissolve in water, such as amine salts and those containing carbon in R3 and R4 in formula [1], are used in emulsions or oil-based cutting oils. Furthermore, since all of the rust preventive agents of the present invention have low foaming properties, they do not foam when used in emulsions or aqueous solutions, and therefore do not reduce the rust preventive effect or be difficult to handle due to foaming. Furthermore, it provides a sufficient rust prevention effect even in small amounts without mixing other inorganic or organic rust preventives, and is effective against wet chips (cast iron powder), which is almost impossible with other rust preventives. It has a wide range of rust prevention effects, such as being able to effectively prevent rust on both steel plates in a wet box (JIS).

Next, the present invention will be explained in more detail with reference to Examples.

Note that all figures in the middle part of the examples are parts by weight. Example 1 250 parts of bis(4-oxyphenyl)sulfone, 96 parts of caustic soda, and 80 parts of water were placed in a reaction vessel equipped with a condenser and a dehydrator and heated to melt.

When it reaches 90 to 95 qo, add 30 to 60 parts of a solution consisting of 257 parts of sodium monochloroacetate and 50 parts of water.
The mixture was added dropwise over a period of minutes, and the mixture was left to react at this temperature for 3 hours.

After cooling, the resulting dicarboxylic acid is acidified with sulfuric acid to precipitate, and is washed with water in a furnace to obtain a white powder of bis(4-oxyphenyl)sulfon-○,0-diacetic acid. Next, 10 parts of this bis(4-oxyphenyl)sulfone-○,0-diacetic acid, 78 parts of trietanoamine, and 415 parts of water are heated and mixed to obtain a rust inhibitor containing about 30% of the active ingredient. Example 2 228 parts of 8,8-bis(4-oxyphenyl)propane, 28 parts of sodium monochloroacetate, 20 parts of methanol, and 30 parts of water were placed in the same reaction vessel as in Example 1, and
After heating to 0 to 85 qo to obtain a transparent solution, a solution of 105 parts of caustic soda and 20 parts of water is added dropwise over 30 to 60 minutes, and the mixture is further heated at this temperature for 3 hours.

After cooling, it is acidified with sulfuric acid to precipitate the generated dicarboxylic acid, and is washed with water in a furnace to obtain a white powder of 8,3-bis(4-oxyphenyl)propane-0,0-diacetic acid. Next, this 6,P-bis(4-oxyphenyl)propane-
10 parts of 0,0-diacetic acid, 85 parts of triethanolamine, and 432 parts of water were mixed to obtain a rust preventive containing about 30% of the active ingredient. Example 3 From 198 parts of bis(4-oxyphenyl)methane, 192 parts of caustic soda, 98 parts of water, and 22 parts of chloropropionic acid, 10 parts of bis(4-oxyphenyl)methane was prepared in the same manner as in Example 1. ,0-dipropiosoic acid is obtained.

Next, this bis(4-oxyphenylmethane-0,0-
100 parts of dipropionic acid, 25 parts of caustic soda, 29 parts of water
Mix 1 part and mix to obtain a rust preventive agent containing about 30% of the active ingredient. Comparative Example 1: 10 parts of benzoic acid, 117 parts of trietanoamine, and 506 parts of water were heated to reduce the active ingredient to about 30%.
Obtain a rust inhibitor.

Comparative Example 2 100 parts of oleic acid, 51 parts of triethanolamine, and 352 parts of water are mixed to obtain a rust inhibitor containing about 30% of active ingredients.

A 1% aqueous solution of the active ingredient was prepared from each of the rust preventives shown in the Examples and Comparative Examples, and a steel plate of SPCC-1 (
Using 60 x 80 x 1 skin), 49 soil 1
°C, relative humidity 95% or more, air intake amount Iso 6.5 Soil 110
．． A rust generation test was conducted under the condition of 5 nights/torr.

This test method is based on JIS-K-2246 (rust preventive oil wet test), and the determination of the degree of rust occurrence is also based on JIS-K-2246 (rust prevention oil wet test).
IS-K-2246 (Rust prevention oil rust occurrence measurement method)
I followed. In addition, the measurement of superfoaming properties was based on the Ross-Clark method.

That is, 200 m/m of an aqueous rust preventive solution containing 1% of the active ingredient is poured into a cylinder with an inner diameter of 50 m/m and a height of 1000 m/m, and a glass filter with a diameter of 40 to 5 m/m is filtered through a glass filter with a diameter of 500 m/m.
n of air was continuously blown into the tube, and the height of the bubbles at 2000 mm after 60 seconds was measured. These results are shown in Table 1. Table-1

Claims (1)

[Claims] 1. A rust preventive agent containing an alkali salt of carboxylic acids represented by the general formula ▲ Numerical formula, chemical formula, table, etc. as an essential component. (In the formula, R_1 and R_2 are alkylene groups having 1 to 6 carbon atoms, and X is an SO_2 group or an alkylene group having 1 to 5 carbon atoms, and this alkylene group may have a lower alkyl side chain having 4 or less carbon atoms. , R_3, R_4 are alkyl groups having 1 to 4 carbon atoms, and m and n are 0 or integers of 1 to 3, respectively.)