JPWO2008123453A1 - Metal corrosion inhibitor composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a metal corrosion inhibitor composition having an excellent metal corrosion prevention effect and a low environmental load. The present invention comprises at least two selected from surfactants or salts thereof; organic acids having 4 or more carbon atoms or salts thereof; phosphorus-containing compounds or salts thereof; and sulfur-containing compounds or salts thereof. A metal corrosion inhibitor composition is provided. The present invention also provides a method for preventing metal corrosion, characterized by treating a metal with a metal corrosion inhibitor composition.

Description

  The present invention relates to a metal corrosion inhibitor that prevents corrosion of metals, particularly ferrous metals. More specifically, the present invention relates to a water-soluble metal corrosion inhibitor that has a synergistic effect on preventing corrosion of ferrous metals.

Conventionally, treatments using various inorganic and organic substances have been performed in order to suppress corrosion of ferrous metals. Borate, phosphate, nitrite, chromate, etc. are known as representative inorganic substances having rust preventive action, and organic substances include fatty acid, thiourea, amine, polyhydric alcohol, etc. Is mentioned.
Today's metal corrosion inhibitors are desired to have not only excellent rust prevention effects, but also reduced toxicity or environmental impact. As a rust inhibitor having relatively low toxicity, for example, Patent Document 1 discloses a rust inhibitor obtained by blending a condensation reaction product of alkanolamine and boric acid and an organic acid. Moreover, patent document 2 is disclosing the rust preventive agent which consists of a reaction product of boric acid and diethanolamine, and the mixture of carboxylic acid. However, such a rust preventive agent has a high cost due to the use of a condensation reaction product of alkanolamine and boric acid, and the rust preventive effect exhibited is not sufficient.

On the other hand, as a rust preventive composed of two or more organic compounds, for example, a rust preventive using a combination of carboxylic acid and amine, a rust preventive using a combination of alcohol and amine, or an amine having a thiol group and polyaspartic acid. A combined rust inhibitor has been developed. However, since these rust preventive agents contain an amine in the molecule, there is a problem of wastewater treatment. Furthermore, there was room for improvement in the rust prevention effect.
Japanese Patent Publication No.58-44746 Japanese Patent Publication No.62-3235 JP-A-5-148670 JP-A-6-316780 JP-A-10-130873 Japanese Patent Laid-Open No. 11-92976 JP 2001-89878 A JP-A-48-71335 JP-A-48-71337 JP 55-44599 A JP 58-213884 A JP 59-1000027 A JP-A-62-2235

  An object of this invention is to provide the metal corrosion inhibitor composition which is excellent in the metal corrosion prevention effect and has a low environmental load.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a surfactant or a salt thereof; an organic acid having 4 or more carbon atoms or a salt thereof; a phosphorus-containing compound or a salt thereof; and a sulfur-containing compound or a salt thereof. It was found that the rust prevention effect is synergistically improved by using at least two kinds selected from the group consisting of: The present invention has been completed based on such findings.

That is, the present invention provides the following aspects of the invention:
Item 1. (i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) A metal corrosion inhibitor composition comprising 2, 3, or 4 selected from at least one of a sulfur-containing compound or a salt thereof.

Item 2. The surfactant is
The following formula (1)
D _WO = γ _SO −γ _SW = γ _WO cos θ (1)
D _WO : substitution energy, γ _SO : metal / oil surface tension, γ _SW : metal / water surface tension,
Item [Claim 1] wherein [gamma] _WO : surface tension between water / oil, [theta]: receding contact angle, each surface tension is a surfactant having a negative value of substitution energy _DWO expressed by measurement at 25 [deg.] C. Metal corrosion inhibitor composition.

  Item 3. Item 3. The metal corrosion inhibitor composition according to Item 1 or 2, wherein the surfactant is a sorbitan esterified product, a sorbitol esterified product, or a polyglycerin esterified product.

  Item 4. Item 4. The metal corrosion inhibitor composition according to any one of Items 1 to 3, wherein the organic acid having 4 or more carbon atoms is a carboxylic acid having 4 or more carbon atoms.

  Item 5. Item 5. The metal corrosion inhibitor composition according to Item 4, wherein the carboxylic acid having 4 or more carbon atoms is a carboxylic acid having 4 to 15 carbon atoms.

  Item 6. The phosphorus-containing compound is represented by the following general formula (2):

[However, R ¹ represents a linear or branched alkyl group having 2 to 15 carbon atoms which may have an aryl group.
l represents an integer of 0-20.
When l is 1, R ² represents a bond or a linear or branched alkylene group having 1 to 4 carbon atoms.
When l is 2 to 20, R ² represents a linear or branched alkylene group having 2 to 4 carbon atoms. ]
Item 6. The metal corrosion inhibitor composition according to any one of Items 1 to 5, which is a compound represented by:

  Item 7. The sulfur-containing compound has the following general formula (3):

[In Formula (3), Y is the following formula (y1) optionally substituted with a sulfur atom or a hydroxyl group:

The group represented by these is shown.
m shows 1-3.
R ^a is a hydroxyl group or the following general formula (a);

(In general formula (a), R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom; an alkyl group optionally substituted with a hydroxyl group; or an aryl group optionally substituted with a hydroxyl group. R ⁴ and R ⁵ may form a carbonyl group together with the carbon atoms to which they are bonded.)
The group represented by these is shown.
R ³ represents a bond; an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; an arylene group which may be substituted with a hydroxyl group or a carboxyl group A monoether group optionally substituted with a hydroxyl group or a carboxyl group; or a polyether group optionally substituted with a hydroxyl group or a carboxyl group.
R ^b represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group or a carboxyl group; an aryl group which may be substituted with a hydroxyl group or a carboxyl group; or the following general formula (b):

(In the formula (b), R ⁶ is an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; a substituent which is substituted with a hydroxyl group or a carboxyl group. An arylene group which may be substituted; a monoether group which may be substituted with a hydroxyl group or a carboxyl group; or a polyether group which may be substituted with a hydroxyl group or a carboxyl group.
R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group; or an aryl group which may be substituted with a hydroxyl group.
Here, R ⁷ and R ⁸ may form a carbonyl group together with the carbon atoms to which they are bonded. )
The group represented by these is shown.
However, when ^Rb represents a hydrogen atom, Y represents a group represented by the formula (y1). ]
Item 7. The metal corrosion inhibitor composition according to any one of Items 1 to 6, which is a compound represented by:

  Item 8. Sulfur-containing compounds are 2-benzothiazolylthioacetic acid, 4-methyl-2-benzothiazolylthioacetic acid, 6-amino-2-benzothiazolylthioacetic acid, 3- (2-benzothiazolylthio) -propionic acid 3- (4-Methyl-2-benzothiazolylthio) -propionic acid, 3- (6-amino-2-benzothiazolylthio) -propionic acid, 3- (4,6-dimethyl-2-benzothia Zolylthio) -propionic acid, 2- (2-benzothiazolylthio) -propionic acid, 2- (4-methyl-2-benzothiazolylthio) -propionic acid, 5- (2-benzothiazolylthio)- Valeric acid, 3- (2-benzothiazolylthio) valeric acid, 5- (4-methyl-2-benzothiazolylthio) -valeric acid, 3- (2-benzothiazolylthio) -acrylic acid, 3- (4-me Ru-2-benzothiazolylthio) -propionic acid, 4- (2-benzothiazolylthio) -butyric acid, 4- (4-methyl-2-benzothiazolylthio) -butyric acid, 4- (6-amino- Item 1 selected from the group consisting of 2-benzothiazolylthio) -butyric acid, 2- (2-benzothiazolylthio) -benzoic acid, 2- (4-methyl-2-benzothiazolylthio) -benzoic acid Metal corrosion inhibitor composition in any one of -7.

Item 9. (i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) The metal corrosion inhibitor composition according to any one of items 1 to 8, which comprises 3 or 4 selected from at least one of a sulfur-containing compound or a salt thereof.

Item 10. (i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) The metal corrosion inhibitor composition according to any one of Items 1 to 9, wherein the composition contains at least one of a sulfur-containing compound or a salt thereof.

  Item 11. Item 11. A method for preventing metal corrosion, comprising treating a metal with the metal corrosion inhibitor composition according to any one of Items 1 to 10.

  The metal corrosion inhibitor composition according to the present invention exhibits a sufficient anti-corrosion effect at a lower concentration by exhibiting a synergistic anti-corrosion effect. Therefore, according to the present invention, an industrially useful metal corrosion inhibitor composition can be provided without using a substance such as an amine that is harmful to the environment.

FIG. 1 is a graph showing the results of Example 1. FIG. 2 is a graph showing the results of Example 2. FIG. 3 is a graph showing the results of Example 3. FIG. 4 is a graph showing the results of Example 4. FIG. 5 is a graph showing the results of Example 19. FIG. 6 is a graph showing the results of Example 20. FIG. 7 is a graph showing the results of Example 21. FIG. 8 is a graph showing the results of Example 22. FIG. 9 is a graph showing the results of Example 23. FIG. 10 is a graph showing the results of Example 24. FIG. 11 is a graph showing the results of Example 25. FIG. 12 is a graph showing the results of Example 26. FIG. 13 is a graph showing the results of Example 27. FIG. 14 is a graph showing the results of Example 28. FIG. 15 is a graph showing the results of Example 34. FIG. 16 is a graph showing the results of Example 35. FIG. 17 is a graph showing the results of Example 36. FIG. 18 is a graph showing the results of Example 37.

  Hereinafter, the present invention will be described in detail. The metal corrosion inhibitor composition according to the present invention comprises at least 2 selected from surfactants or salts thereof; organic acids having 4 or more carbon atoms or salts thereof; phosphorus-containing compounds or salts thereof; and sulfur-containing compounds or salts thereof. It contains seeds.

The metal corrosion inhibitor composition according to the present invention is preferably
A combination of a surfactant or a salt thereof and an organic acid having 4 or more carbon atoms or a salt thereof;
A combination of a surfactant or a salt thereof and a phosphorus-containing compound or a salt thereof; or a combination of a phosphorus-containing compound or a salt thereof and a sulfur-containing compound or a salt thereof.

As surfactant or its salt, following formula (1)
D _WO = γ _SO −γ _SW = γ _WO cos θ (1)
D _WO : substitution energy, γ _SO : metal / oil surface tension, γ _SW : metal / water surface tension,
γ _WO : surface tension between water / oil, θ: receding contact angle, and each surface tension is preferably a surfactant or a salt thereof in which the value of substitution energy D _WO expressed by measurement at 25 ° C. is negative. Examples of surfactants value is negative substituted energy D _WO, sorbitan monopalmitate (-7.9erg / cm ²⁾ [in parentheses indicate the values of the substitution energy. The same applies to the following. ], Dioctyl phosphite (-10.0 erg / cm < ² >), alkyl phosphate (-10.5 erg / cm < ² >), etc., but are not limited thereto.

  Examples of the surfactant include a sorbitan esterified product, a sorbitol esterified product, or a polyglycerol esterified product.

  Examples of sorbitan esterified products include sorbitan monofatty acid esters, sorbitan difatty acid esters, sorbitan trifatty acid esters, polyoxyethylene sorbitan monofatty acid esters, polyoxyethylene sorbitan difatty acid esters, polyoxyethylene sorbitan trifatty acid esters, and the like. . Specifically, examples of sorbitan mono fatty acid esters include sorbitan mono n-nonanoate, sorbitan monoisononanoate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monostearate And neodecanoic acid esters.

  Examples of sorbitan difatty acid esters include sorbitan di n-nonanoate, sorbitan diisononanoate, sorbitan dilaurate, sorbitan dineodecanoate, sorbitan dipalmitate, sorbitan distearate, sorbitan dioleate, and the like. .

  Examples of sorbitan trifatty acid esters include sorbitan tri-n-nonanoate, sorbitan triisononanoate, sorbitan trilaurate, sorbitan trineodecanoate, sorbitan tripalmitate, sorbitan tristearate, sorbitan trioleate, etc. It is done.

  Examples of polyoxyethylene sorbitan mono-fatty acid ester include polyoxyethylene (6) sorbitan mono-n-nonanoic acid ester (in parentheses indicate the number of moles of ethylene oxide added. The same applies hereinafter), polyoxyethylene (20) Sorbitan mono n-nonanoate, polyoxyethylene (6) sorbitan monoisononanoate, polyoxyethylene (20) sorbitan monoisononanoate, polyoxyethylene (6) sorbitan monolaurate, polyoxyethylene (20) sorbitan Monolaurate, polyoxyethylene (6) sorbitan mononeodecanoate, polyoxyethylene (20) sorbitan mononeodecanoate, polyoxyethylene (6) sorbitan monopalmitate, polyoxyethylene (2 ) Sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (6) sorbitan monooleate, polyoxyethylene (20) sorbitan monooleate Is mentioned.

Examples of polyoxyethylene sorbitan difatty acid esters include polyoxyethylene (6) sorbitan di-n-nonanoic acid ester, polyoxyethylene (20) sorbitan di-n-nonanoic acid ester, polyoxyethylene (6) sorbitan diisononanoic acid Ester polyoxyethylene (20) sorbitan diisononanoic acid ester, polyoxyethylene (6) sorbitan dilaurate, polyoxyethylene (20) sorbitan dilaurate polyoxyethylene (6) sorbitan dineodecanoate, polyoxyethylene (20) sorbitan di Neodecanoic acid ester, polyoxyethylene (6) sorbitan dipalmitate, polyoxyethylene (20) sorbitan dipalmitate, polyoxyethylene (6) sorbitan distearate, polyoxy Ethylene (20) sorbitan distearate, polyoxyethylene (6) sorbitan dioleate, polyoxyethylene (20) sorbitan dioleate and the like.

  Examples of polyoxyethylene sorbitan trifatty acid esters include polyoxyethylene (6) sorbitan tri-n-nonanoic acid ester, polyoxyethylene (20) sorbitan tri-n-nonanoic acid ester, polyoxyethylene (6) sorbitan triisononanoic acid Ester, polyoxyethylene (20) sorbitan triisononanoate, polyoxyethylene (6) sorbitan trilaurate, polyoxyethylene (20) sorbitan trilaurate, polyoxyethylene (6) sorbitan trineodecanoate, polyoxy Ethylene (20) sorbitan trineodecanoate, polyoxyethylene (6) sorbitan tripalmitate, polyoxyethylene (20) sorbitan tripalmitate, polyoxyethylene (6) sorbita Tristearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (6) sorbitan trioleate and polyoxyethylene (20) sorbitan trioleate and the like.

  Examples of sorbitol esterified products include sorbitol monofatty acid ester, sorbitol difatty acid ester, sorbitol trifatty acid ester, sorbitol tetrafatty acid ester, polyoxyethylene sorbitol monofatty acid ester, polyoxyethylene sorbitol difatty acid ester, polyoxyethylene sorbitol trifatty acid Examples thereof include esters and polyoxyethylene sorbitol tetrafatty acid esters. Specifically, sorbitol monolaurate, sorbitol dilaurate, sorbitol trilaurate, sorbitol tetralaurate, polyoxyethylene (6) sorbitol tetralaurate, polyoxyethylene (20) sorbitol tetralaurate, polyoxyethylene (30 ) Sorbitol tetralaurate, sorbitol monopalmitate, sorbitol dipalmitate, sorbitol tripalmitate, sorbitol tetrapalmitate, polyoxyethylene (6) sorbitol tetrapalmitate, polyoxyethylene (20) sorbitol tetrapalmitate, polyoxy Ethylene (30) sorbitol tetrapalmitate, sorbitol monostearate, sorbitol distearate, sorbitol tristearate Sorbitol tetrastearate, polyoxyethylene (6) sorbitol tetrastearate, polyoxyethylene (20) sorbitol tetrastearate, polyoxyethylene (30) sorbitol tetrastearate, sorbitol monooleate, sorbitol dioleate, sorbitol Examples thereof include trioleate, sorbitol tetraoleate, polyoxyethylene (6) sorbitol tetraoleate, polyoxyethylene (20) sorbitol tetrasoleate, polyoxyethylene (30) sorbitol tetraoleate.

  Examples of polyglycerin esterified products include polyglycerin monofatty acid ester, polyglycerin difatty acid ester, polyglycerin trifatty acid ester and the like. Specifically, polyglycerin esters such as decaglycerin monolaurate, decaglycerin monostearate, decaglycerin distearate, decaglycerin octastearate, decaglycerin monooleate, decaglycerin dioleate, decaglycerin trioleate However, it is not limited to these.

  When these surfactants are used, one kind may be used alone, or two or more kinds may be appropriately mixed and used.

  Examples of the organic acid having 4 or more carbon atoms include carboxylic acids having 4 or more carbon atoms (for example, 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms).

  Specifically, examples of the compound when the organic acid is a carboxylic acid include saturated fatty acids, unsaturated fatty acids, aromatic fatty acids, dibasic acids and the like (preferably saturated fatty acids).

  Examples of saturated fatty acids include caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, decanoic acid, neodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid Examples thereof include acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccellic acid.

  Examples of the unsaturated fatty acid include undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, ricinoleic acid and stearic acid. .

  Examples of aromatic fatty acids include benzoic acid, toluic acid, ethyl benzoic acid, and p-tert-butyl benzoic acid.

  Examples of the dibasic acid include dodecanedioic acid, sebacic acid, adipic acid, suberic acid, and azelaic acid.

  These organic acids may be used alone or in combination of two or more.

As the phosphorus-containing compound, the following general formula (2)
Formula (2)

[However, R ¹ represents a linear or branched alkyl group having 2 to 15 (preferably 2 to 12) carbon atoms which may have an aryl group.
l represents an integer of 0-20.
When l is 1, R ² represents a bond or a linear or branched alkylene group having 1 to 4 carbon atoms.
When l is 2 to 20, R ² represents a linear or branched alkylene group having 2 to 4 carbon atoms. ]
The compound represented by these can be mentioned.

  Here, the linear or branched alkyl group having 2 to 15 carbon atoms includes ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, Examples thereof include a pentadecyl group.

The linear or branched alkyl group having 2 to 15 carbon atoms represented by R ¹ may have 1 to 3 (preferably 1) aryl group.

  Examples of the aryl group include aryl groups having 5 to 14 carbon atoms such as phenyl, naphthyl, biphenyl, and anthracenyl groups.

Here, when the linear or branched alkyl group represented by R ¹ has an aryl group, an alkyl group having 1 to 4 carbon atoms may be further substituted on the aryl group.

When l is 1, examples of the linear or branched alkylene group having 1 to 4 carbon atoms represented by R ² include methylene, ethylene, propylene, butylene, and isobutylene groups.

When l is 2 to 20, examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by R ² include ethylene, propylene, butylene, and isobutylene groups.

  Examples of the phosphorus-containing compound represented by the general formula (2) include alkylphosphonic acid, alkylphosphinic acid, cycloalkylphosphonic acid, cycloalkylphosphinic acid, arylphosphonic acid, arylphosphinic acid, aralkylphosphonic acid, aralkylphosphinic acid And phosphonic acid and phosphinic acid. Specifically, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, n- Dodecylphosphonic acid, 4-tert-butylbenzylphosphonic acid, phenylethylphosphonic acid, phenylbutylphosphonic acid, cyclohexylphosphonic acid, n-pentylphosphinic acid, n-hexylphosphinic acid, n-heptylphosphinic acid, n-octylphosphinic acid , N-nonylphosphinic acid, n-decylphosphinic acid, n-undecylphosphinic acid, n-dodecylphosphinic acid, 4-tert-butylbenzylphosphinic acid, phenylethylphosphinic acid, phenylbutylphosphinic acid, cyclohexylphosphinic acid and these Salt of Including but not being limited thereto.

  These phosphorus-containing compounds may be used alone or in combination of two or more.

  As the sulfur-containing compound, the general formula (3):

[In Formula (3), Y is the following formula (y1) optionally substituted with a sulfur atom or a hydroxyl group;

The group represented by these is shown.
m shows 1-3.
R ^a is a hydroxyl group or the following general formula (a);

(In general formula (a), R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom; an alkyl group optionally substituted with a hydroxyl group; or an aryl group optionally substituted with a hydroxyl group. R ⁴ and R ⁵ may form a carbonyl group together with the carbon atoms to which they are bonded.)
The group represented by these is shown.
R ³ represents a bond; an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; an arylene group which may be substituted with a hydroxyl group or a carboxyl group A monoether group optionally substituted with a hydroxyl group or a carboxyl group; or a polyether optionally substituted with a hydroxyl group or a carboxyl group.
R ^b represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group or a carboxyl group; an aryl group which may be substituted with a hydroxyl group or a carboxyl group; or the following general formula (b):

(In the formula (b), R ⁶ is an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; a substituent which is substituted with a hydroxyl group or a carboxyl group. An arylene group which may be substituted; a monoether group which may be substituted with a hydroxyl group or a carboxyl group; or a polyether group which may be substituted with a hydroxyl group or a carboxyl group.
R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group; or an aryl group which may be substituted with a hydroxyl group.
Here, R ⁷ and R ⁸ may form a carbonyl group together with the carbon atoms to which they are bonded. )
The group represented by these is shown.
However, when ^Rb represents a hydrogen atom, Y represents a group represented by the formula (y1). ]
The compound represented by these can be mentioned.

  When the group represented by the formula (y1) is substituted with a hydroxyl group, the number of substituents is usually about 1 to 2, preferably about 1.

The alkyl group represented by R ⁴ and R ⁵ may be linear or branched and may be substituted with a hydroxyl group. Examples of the alkyl group represented by R ⁴ and R ⁵ include an alkyl group having 1 to 12 carbon atoms, preferably about 1 to 4 carbon atoms. Specifically, a methyl group, an ethyl group, and the like. N-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, 1-ethylpropyl group, isopentyl group, neopentyl group, n-hexyl group, 1 2,2-trimethylpropyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, isohexyl group, 3-methylpentyl group and the like. The alkyl groups represented by R ⁴ and R ⁵ may be substituted with about 1 to 4 hydroxyl groups, preferably about 1 hydroxyl group.

Examples of the aryl group represented by R ⁴ and R ⁵ include, but are not limited to, a phenyl group, and the number of these groups is usually about 1 to 4, preferably about 1. It may be substituted with a hydroxyl group.

The alkylene group represented by R ³ and R ⁶ may be linear or branched, and may be substituted with a hydroxyl group or a carboxyl group. The number of carbon atoms of the alkylene group represented by ^{R 3} and ^{R 6} is preferably 1 to 12, more preferably 1-4. Examples of the alkylene group represented by R ³ and R ⁶ include methylene group, ethylene group, trimethylene group, 2-methyltrimethylene group, 2,2-dimethylethylene group, 2,2-dimethyltrimethylene group, 1- Examples include methyltrimethylene group, methylmethylene group, ethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, but are not limited thereto, and these groups are usually about 1 to 4, Preferably, it may be substituted with about one hydroxyl group or carboxyl group.

The alkenylene group represented by R ³ and R ⁶ may be linear or branched, and may be substituted with a hydroxyl group or a carboxyl group. Moreover, it is preferable that carbon number of the alkenylene group shown by R < ³ > and R < ⁶ > is 2-12, More preferably, it is 2-4. Examples of alkenylene groups represented by R ³ and R ⁶ include vinylene group, 1-propenylene group, 1-methyl-1-propenylene group, 2-methyl-1-propenylene group, 2-propenylene group and 2-butenylene group. 1-butenylene group, 3-butenylene group, 2-pentenylene group, 1-pentenylene group, 3-pentenylene group, 4-pentenylene group, 1,3-butadienylene group, 1,3-pentadienylene group, 2-pentene-4 -Inylene group, 2-hexenylene group, 1-hexenylene group, 5-hexenylene group, 3-hexenylene group, 4-hexenylene group, 3,3-dimethyl-1-propenylene group, 2-ethyl-1-propenylene group 1,3,5-hexatrienylene group, 1,3-hexadienylene group, 1,4-hexadienylene group, and the like. Rather than being limited to, these groups are usually about 1-6, preferably may be substituted by one order of hydroxyl group or carboxyl group.

The arylene group represented by R ³ and R ⁶ may be substituted with a hydroxyl group or a carboxyl group. The number of carbon atoms of the arylene group represented by ^{R 3} and ^{R 6} is preferably 6 to 14, more preferably 6 to 10. Examples of the arylene group represented by R ³ and R ⁶ include phenylene, naphthylene, anthrylene, phenanthrylene, and the like, but are not limited thereto, and these groups are usually about 1 to 10, Preferably, it may be substituted with about 1 to 2 hydroxyl groups or carboxyl groups.

Examples of the monoether represented by R ³ and R ⁶ include those in which one oxygen is contained in the alkylene group. Specific examples of monoethers represented by R ³ and R ⁶ include —C ₂ H ₄ O—CH ₂ —, —C ₃ H ₆ O—C ₂ H ₄ —, —C ₄ H ₈ O—C. Examples thereof include, but are not limited to, ₃ H _6- and the like, and these groups may be substituted with usually about 1 to 8, preferably about 1, hydroxyl group or carboxyl group.

Examples of the polyether represented by R ³ and R ⁶ include those in which two or more oxygen atoms are contained in the alkylene group. Specific examples of the polyether represented by R ³ and R ⁶ include — (C ₂ H ₄ O) _n1 —CH ₂ — (n1 = 2 to 5), — (C ₃ H ₆ O) _n2 —C ₂ H. ₄ - (n2 = _2~3) and others as you mentioned, rather than being limited to, these groups are usually about 1-6, is preferably substituted by one order of hydroxyl group or carboxyl group It may be.

The alkyl group represented by R ^b may have a straight chain or a branch, and may be substituted with a hydroxyl group or a carboxyl group. Examples of such an alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably about 4 to 12 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, 1-ethylpropyl group, isopentyl group, neopentyl group, n-hexyl group, 1,2,2-trimethylpropyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, isohexyl group, 3-methylpentyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like are included. Further, these alkyl groups represented by R ^b are usually substituted with about 1 to 6, preferably about 1 hydroxyl group or carboxyl group.

Examples of the aryl group represented by ^Rb include, but are not limited to, a phenyl group, a benzyl group, a toluyl group, an ethylphenyl group, a styryl group, a tert-butylphenyl group, a naphthyl group, and an anthryl group. Instead, these groups may be substituted with about 1 to 10, preferably about 1 to 2 hydroxyl groups or carboxyl groups.

The alkyl group represented by R ⁷ and R ⁸ may have a straight chain or a branch, and may be substituted with a hydroxyl group. Examples of the alkyl group represented by R ⁷ and R ⁸ include an alkyl group having 1 to 12 carbon atoms, preferably about 1 to 6 carbon atoms. Specifically, a methyl group, an ethyl group, and the like. N-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, 1-ethylpropyl group, isopentyl group, neopentyl group, n-hexyl group, 1 2,2-trimethylpropyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, isohexyl group, 3-methylpentyl group and the like. The alkyl groups represented by these R ⁷ and R ^8, usually about 1-8, preferably may be substituted with 1-4 of about hydroxyl groups. Examples of the aryl group represented by R ⁷ and R ⁸ include, but are not limited to, a phenyl group, and the number of these groups is usually about 1 to 6, preferably about 1. It may be substituted with a hydroxyl group.

  When such a compound represented by the general formula (3) is a monocarboxylic acid or a salt thereof, the carbon number of the monocarboxylic acid is preferably 7 to 15. Moreover, when the compound shown by General formula (3) is dicarboxylic acid, Preferably, carbon number of the said dicarboxylic acid is 6-10. This is because if the carbon number is smaller than the above range, the rust prevention power is weak, and if the carbon number is larger than the above range, the solubility in water becomes low, and as a result, sufficient rust prevention power cannot be obtained. Because.

  Examples of the compound represented by the general formula (3) include alkylthiocarboxylic acid, arylthiocarboxylic acid, alkyl or arylthiodicarboxylic acid, and optionally substituted benzothiazolylthiocarboxylic acid.

  Specifically, examples of the alkylthiocarboxylic acid include n-pentylthioglycolic acid, n-hexylthioglycolic acid, cyclohexylthioglycolic acid, n-heptylthioglycolic acid, n-octylthioglycolic acid, 2-ethylhexylthio Glycolic acid, n-nonylthioglycolic acid, n-decylthioglycolic acid, n-undecylthioglycolic acid, n-dodecylthioglycolic acid, n-butylthiopropionic acid, n-pentylthiopropionic acid, n-hexylthio Propionic acid, cyclohexylthiopropionic acid, n-heptylthiopropionic acid, n-octylthiopropionic acid, 2-ethylhexylthiopropionic acid, n-nonylthiopropionic acid, n-decylthiopropionic acid, n-undecylthiopropionic acid , N-dode Ruthiopropionic acid, n-butylthiolactic acid, n-pentylthiolactic acid, n-hexylthiolactic acid, cyclohexylthiolactic acid, n-heptylthiolactic acid, n-octylthiolactic acid, 2-ethylhexylthiolactic acid, n-nonylthiolactic acid, n-decylthiolactic acid, n -Undecylthiolactic acid, n-dodecylthiolactic acid, n-propylthiobutanoic acid, n-butylthiobutanoic acid, n-pentylthiobutanoic acid, n-hexylthiobutanoic acid, cyclohexylthiobutanoic acid, n-heptylthiobutanoic acid, n -Octylthiobutanoic acid, 2-ethylhexylthiobutanoic acid, n-nonylthiobutanoic acid, n-decylthiobutanoic acid, n-undecylthiobutanoic acid, n-ethylthiopentanoic acid, n-propylthiopentanoic acid, n-butyl Thiopentanoic acid, n-pentylthiopentanoic acid, -Hexylthiopentanoic acid, cyclohexylthiopentanoic acid, n-heptylthiopentanoic acid, n-octylthiopentanoic acid, 2-ethylhexylthiopentanoic acid, n-nonylthiopentanoic acid, n-decylthiopentanoic acid, n-methylthiohexane Acid, n-ethylthiohexanoic acid, n-propylthiohexanoic acid, n-butylthiohexanoic acid, n-pentylthiohexanoic acid, n-hexylthiohexanoic acid, cyclohexylthiohexanoic acid, n-heptylthiohexanoic acid, n -Octylthiohexanoic acid, 2-ethylhexylthiohexanoic acid, n-nonylthiohexanoic acid, n-methylthioheptanoic acid, n-ethylthioheptanoic acid, n-propylthioheptanoic acid, n-butylthioheptanoic acid, n-penty Ruthioheptanoic acid, n-hexylthioheptanoic acid , Cyclohexylthioheptanoic acid, n-heptylthioheptanoic acid, n-octylthioheptanoic acid, 2-ethylhexylthioheptanoic acid, n-methylthiooctanoic acid, n-ethylthiooctanoic acid, n-propylthiooctanoic acid, n-butyl Thiooctanoic acid, n-pentylthiooctanoic acid, n-hexylthiooctanoic acid, cyclohexylthiooctanoic acid, n-heptylthiooctanoic acid, phenylthiooctanoic acid, n-methylthiononanoic acid, n-ethylthiononanoic acid, n-propylthio Nonanoic acid, n-butylthiononanoic acid, n-pentylthiononanoic acid, n-hexylthiononanoic acid, cyclohexylthiononanoic acid, n-methylthiodecanoic acid, n-ethylthiodecanoic acid, n-propylthiodecanoic acid, n-butyl Thiodecanoic acid, n-pentylthiodecanoic acid n-methylthioundecanoic acid, n-ethylthioundecanoic acid, n-propylthioundecanoic acid, n-butylthioundecanoic acid, n-methylthiododecanoic acid, n-ethylthiododecanoic acid, n-propylthiododecanoic acid, n-methylthio Examples include, but are not limited to, tridecanoic acid, n-ethylthiotridecanoic acid, n-methylthiotetradecanoic acid, and the like, and lithium salts, sodium salts, and potassium salts thereof.

Examples of arylthiocarboxylic acids include 4-tert-butylbenzylthioglycolic acid, phenylethylthioglycolic acid, phenylthioglycolic acid, 4-tert-butylbenzylthiopropionic acid, phenylethylthiopropionic acid, phenylthiopropionic acid, 4-tert-butylbenzylthiolactic acid, phenylethylthiolactic acid, phenylthiolactic acid, 4-tert-butylbenzylthiobutanoic acid, phenylethylthiobutanoic acid, phenylthiobutanoic acid, phenylethylthiopentanoic acid, phenylthiopentanoic acid, phenyl Ethylthiohexanoic acid, phenylthiohexanoic acid, phenylethylthioheptanoic acid, phenylthioheptanoic acid, phenylthiononanoic acid, 2-methylthiobenzoic acid, 4-methylthiobenzoic acid, 2-ethylthiobenzoate Acid, 4-ethylthiobenzoic acid, 2-propylthiobenzoic acid, 4-propylthiobenzoic acid, 2-butylthiobenzoic acid, 4-butylthiobenzoic acid, 2-pentylthiobenzoic acid, 4-pentylthiobenzoic acid, 2-hexylthiobenzoic acid, 4-hexylthiobenzoic acid, 2-heptylthiobenzoic acid, 4-heptylthiobenzoic acid, 2-octylthiobenzoic acid, 4-octylthiobenzoic acid, 2-thiophenecarboxylic acid, 3-thiophenecarboxylic acid, 2-thienylacetic acid, 3-thienyl Acetic acid, 3- (2-thienyl) propionic acid, 3- (2-thienyl) butanoic acid, 2-hydroxythioanisole, 4-methylthiophenol, (4,4′dihydroxy) diphenylthioether, and lithium salts thereof, sodium Salt, potassium salt, etc. But it is not.
Examples of alkyl or aryl thiodicarboxylic acids include thiodipropionic acid, thiodibutanoic acid, thiodipentanoic acid, thiodihexanoic acid, 3-thiaoctanedioic acid, 4-thiaoctanedioic acid, 3-thianonanedioic acid, 4-thianonanedioic acid, 3 -Thiadecanedioic acid, 4-thiadecanedioic acid, 5-thiadecanedioic acid, 3-thiaundecanedioic acid, 4-thiaundecanedioic acid, 5-thiaundecanedioic acid, 3-thiadecanedioic acid, 4-thiadecanedioic acid, 5-thiadecanedioic acid, 6-thiadecanedioic acid, 3-thiatetradecanedioic acid, 4-thiapentadecanedioic acid, 4,8-dithiadecanedioic acid, methylthiomalic acid, ethylthiomalic acid, n-propylthiomalic acid, isopropylthio Malic acid, n-butylthiomalic acid, t-butylthiomalic acid, n-pentylthio Malic acid, n-hexylthiomalic acid, cyclohexylthiomalic acid, phenylthiomalic acid, n-pentylthiomalic acid, n-octylthiomalic acid, 2-ethylhexylthiomalic acid, n-nonylthiomalic acid, n-decylthiomalic acid, Examples include, but are not limited to, 2,5-thiophenedicarboxylic acid, and the like, and lithium salts, sodium salts, and potassium salts thereof.

  Examples of the optionally substituted benzothiazolylthiocarboxylic acid include 2-benzothiazolylthioacetic acid, 4-methyl-2-benzothiazolylthioacetic acid, 6-amino-2-benzothiazolylthioacetic acid, 3 -(2-benzothiazolylthio) -propionic acid, 3- (4-methyl-2-benzothiazolylthio) -propionic acid, 3- (6-amino-2-benzothiazolylthio) -propionic acid, 3 -(4,6-dimethyl-2-benzothiazolylthio) -propionic acid, 2- (2-benzothiazolylthio) -propionic acid, 2- (4-methyl-2-benzothiazolylthio) -propionic acid 5- (2-benzothiazolylthio) -valeric acid, 3- (2-benzothiazolylthio) valeric acid, 5- (4-methyl-2-benzothiazolylthio) -valeric acid, 3- (2 − Nzothiazolylthio) -acrylic acid, 3- (4-methyl-2-benzothiazolylthio) -propionic acid, 4- (2-benzothiazolylthio) -butyric acid, 4- (4-methyl-2- Benzothiazolylthio) -butyric acid, 4- (6-amino-2-benzothiazolylthio) -butyric acid, 2- (2-benzothiazolylthio) -benzoic acid, 2- (4-methyl-2-benzothia Zolylthio) -benzoic acid and the like and lithium salts, sodium salts and potassium salts thereof, but are not limited thereto. These organic substances may be used alone or in combination of two or more.

  Moreover, when the compound containing the thioether represented by the said General formula (3) is alcohol, carbon number of the said alcohol becomes like this. Preferably it is 4-8. Specific examples of such alcohols include thiodiethanol, thiodipropanol, thiodibutanol, thiodipentanol, 3,6-dithia-1,8-octanediol, methylthioglycerin, ethylthioglycerin, n- Propylthioglycerin, isopropylthioglycerin, n-butylthioglycerin, t-butylthioglycerin, n-pentylthioglycerin, n-hexylthioglycerin, cyclohexylthioglycerin, phenylthioglycerin, n-pentylthioglycerin, n-octylthio Glycerin, 2-ethylhexylthioglycerin, n-nonylthioglycerin, n-decylthioglycerin, n-undecylthioglycerin, n-dodecylthioglycerin, 2-thiophene methanol, 3-thiophene meta Lumpur, ethyl thio ethanol, ethyl thio-propanol, but is not limited thereto.

  These sulfur-containing compounds may be used alone or in combination of two or more.

  In the metal corrosion inhibitor composition of the present invention, when a surfactant or a salt thereof and an organic acid having 4 or more carbon atoms or a salt thereof are combined, the blending ratio is preferably 3:97 to 97: parts by weight. 3, more preferably 10:90 to 90:10. In addition, the synergistic effect with respect to a rust prevention effect is not acquired as the ratio of surfactant or its salt and C4 or more organic acid or its salt is outside the said range of 3: 97-97: 3.

  In the metal corrosion inhibitor composition of the present invention, when combining at least one of a surfactant or a salt thereof and at least one of a phosphorus-containing compound or a salt thereof, the blending ratio is preferably 3:97 to parts by weight. 97: 3, and more preferably 10:90 to 90:10. In addition, when the ratio of at least one of the surfactant or its salt and at least one of the phosphorus-containing compound or its salt is outside the range of 3:97 to 97: 3, a synergistic effect on the rust prevention action cannot be obtained. .

  In the metal corrosion inhibitor composition of the present invention, when combining at least one of a surfactant or a salt thereof and at least one of a sulfur-containing compound or a salt thereof, the blending ratio is preferably from 3:97 to parts by weight. 97: 3, and more preferably 10:90 to 90:10. In addition, when the ratio of at least one of the surfactant or the salt thereof and at least one of the sulfur-containing compound or the salt thereof is out of the range of 3:97 to 97: 3, a synergistic effect on the rust prevention action cannot be obtained. .

  In the metal corrosion inhibitor composition of the present invention, when combining at least one of an organic acid having 4 or more carbon atoms or a salt thereof and at least one of a phosphorus-containing compound or a salt thereof, the blending ratio is preferably in parts by weight. It is 3: 97-97: 3, More preferably, it is 10: 90-90: 10. In addition, when the ratio of at least one of the organic acid having 4 or more carbon atoms or a salt thereof and at least one of the phosphorus-containing compound or the salt thereof is outside the range of 3:97 to 97: 3, a synergistic effect on the rust prevention action. Cannot be obtained.

  In the metal corrosion inhibitor composition of the present invention, when combining at least one of an organic acid having 4 or more carbon atoms or a salt thereof and at least one of a sulfur-containing compound or a salt thereof, the blending ratio is preferably in parts by weight. It is 3: 97-97: 3, More preferably, it is 10: 90-90: 10. In addition, when the ratio of at least one of the organic acid having 4 or more carbon atoms or a salt thereof and at least one of the sulfur-containing compound or the salt thereof is outside the range of 3:97 to 97: 3, a synergistic effect on the rust prevention action. Cannot be obtained.

  In the metal corrosion inhibitor composition of the present invention, when combining at least one of a phosphorus-containing compound or a salt thereof and at least one of a sulfur-containing compound or a salt thereof, the blending ratio is preferably 3:97 to parts by weight. 97: 3, and more preferably 10:90 to 90:10. In addition, if the ratio of at least one of the phosphorus-containing compound or a salt thereof and at least one of the sulfur-containing compound or a salt thereof is outside the range of 3:97 to 97: 3, a synergistic effect on the rust prevention action cannot be obtained. .

  Further, in a preferred embodiment, the present invention provides (i) at least one of a surfactant or a salt thereof; (ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof; (iii) a phosphorus-containing compound or Provided is a metal corrosion inhibitor composition comprising at least one of its salts; and (iv) three or four selected from at least one of a sulfur-containing compound or a salt thereof.

  In the embodiment, the surfactant used or a salt thereof; an organic acid having 4 or more carbon atoms or a salt thereof; a phosphorus-containing compound or a salt thereof; and / or a sulfur-containing compound or a salt thereof; It is the same.

  In a more preferred embodiment, the present invention is characterized by containing a surfactant or a salt thereof; an organic acid having 4 or more carbon atoms or a salt thereof; a phosphorus-containing compound or a salt thereof; and a sulfur-containing compound or a salt thereof. A metal corrosion inhibitor composition is provided.

  In the embodiment, the surfactant used or a salt thereof; an organic acid having 4 or more carbon atoms or a salt thereof; a phosphorus-containing compound or a salt thereof; and a sulfur-containing compound or a salt thereof are the same as described above. is there.

  The metal corrosion inhibitor composition of the present invention comprises an active ingredient surfactant or salt thereof; an organic acid having 4 or more carbon atoms or salt thereof; a phosphorus-containing compound or salt thereof; and / or a sulfur-containing compound or salt thereof only. Or an aqueous solution containing these active ingredients, and if necessary, various additives such as pH adjusters, lubricants, preservatives, emulsifiers, extreme pressure additives, antifoaming agents, and solvents. Can be added as long as the rust prevention effect is not impaired.

  The general blending ratio is based on 100 parts by weight of the total composition of a surfactant or salt thereof as an active ingredient; an organic acid or salt thereof having 4 or more carbon atoms; a phosphorus-containing compound or salt thereof; and a sulfur-containing compound. Alternatively, the salt content is 0.1 to 100 parts by weight. More preferably, it is 1 to 40 parts by weight.

  The metal corrosion inhibitor composition of the present invention can be used by appropriately diluting with water according to the intended use. In use, the metal corrosion inhibitor composition of the present invention comprises a surfactant or salt thereof as an active ingredient; an organic acid having 4 or more carbon atoms or salt thereof; a phosphorus-containing compound or salt thereof; and a sulfur-containing compound or salt thereof. The total weight of the salt is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the diluted aqueous solution. Used.

  The pH of the metal corrosion inhibitor composition of the present invention at the time of use is preferably 6.0 to 12.5, more preferably 7.0 to 12.0. In order to obtain sufficient rust prevention properties, the pH is preferably 6 or more. In consideration of skin irritation that causes rough hands, treatment of waste alkali, which is a specific management industrial waste in waste treatment, and the like, the pH is This is because it is desirably 12.5 or less.

  In the method for preparing the metal corrosion inhibitor composition of the present invention, a surfactant having a negative substitution energy or a salt thereof, an organic acid, and warm water at room temperature to 80 ° C., preferably 30 to 40 ° C. One or more selected from alcohol or a salt thereof is added under stirring and completely dissolved, and then water is added to adjust to a predetermined concentration.

  The metal corrosion inhibitor composition of the present invention prepared in this way can be widely used as a metal corrosion inhibitor that is usually used industrially. For example, when cleaning machine parts, metal parts, etc. It can be used for temporary storage, metal processing (cutting, grinding, plastic processing, etc.), addition to the coolant, and rust prevention in piping systems and tanks.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Evaluation method of rust prevention power 5 g of chips (8-12 mesh) obtained by dry-cutting cast iron (FC250) was collected in a plastic cup with filter paper (40Φm / m, 5C) for Kiriyama. 10 ml of a water-soluble anticorrosive test solution prepared in the above was added to immerse cast iron chips. After sufficiently shaking this, it was allowed to stand for 10 minutes, and then only the test solution of the water-soluble anticorrosive agent was drained by a tilting method and drained. Thereafter, the plastic cup containing the cast iron chips was covered and left in a constant temperature and humidity chamber with an air temperature of 30 ° C. and a humidity of 80%, and the occurrence of rust of the cast iron chips on the filter paper was observed after 15 hours. The criteria for determination are as follows.

"Y": No rust generation "N": Rust generation

Example 1
Weigh n-octylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and n-hexylthiopropionic acid in the weight shown in Table 1 and Table 2 into a 100 ml beaker, add 90 g of water, Caustic soda was added and dissolved to adjust the pH to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 1 shows the composition and results of samples in which no rust was generated, and Table 2 shows the compositions and results of samples in which rust was generated.

  The results of Example 1 are shown in Table 1 and Table 2, respectively. The results of both are shown together in FIG. As shown in Table 2, when n-octyl phosphonic acid or n-hexyl thiopropionic acid is used alone, the minimum concentration required to exert a sufficient anticorrosive effect is n-octyl phosphonic acid. 1.17% by weight and 1.14% by weight for n-hexylthiopropionic acid. As can be seen from FIG. 1, the anticorrosive ability is improved by the combined use of n-octylphosphonic acid and n-hexylthiopropionic acid. Among these, the range which shows a synergistic effect was a case where n-hexyl thiopropionic acid was 10 to 90% with respect to n-octyl phosphonic acid.

  The blending ratio of n-hexylthiopropionic acid (P) and n-octylphosphonic acid (Q), which shows a strong synergistic effect, is expressed by the following formula, and a graph is shown in FIG.

(Example 2)
Weigh n-octylphosphonic acid and sorbitan monolaurate [substitution energy value (erg / cm ² ) = − 7.9] shown in Tables 3 and 4 in a 100 ml beaker, add 90 g of water, and add caustic soda. Was added and dissolved, the pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 3 shows the composition and results of samples in which no rust was generated, and Table 4 shows the compositions and results of samples in which rust was generated.

  The results of Example 2 are shown in Table 3 and Table 4, and both results are shown together in FIG. As shown in Table 4, when n-octylphosphonic acid or sorbitan monolaurate is used alone, the minimum concentration required to exhibit a sufficient antirust effect is 1 for n-octylphosphonic acid. The sorbitan monolaurate did not show a rust-preventing effect even when 2.77% by weight was added. As can be seen from FIG. 2, the rust-preventing power is improved by the combined use of n-octylphosphonic acid and sorbitan monolaurate. Of these, the lower limit concentration at which the synergistic effect of rust prevention by addition of sorbitan monolaurate was 3% or more with respect to n-octylphosphonic acid.

  The blending ratio of n-octylphosphonic acid (P) and sorbitan monolaurate (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

Example 3
Weigh neodecanoic acid and sorbitan monolaurate [substitution energy value (erg / cm ² ) = − 7.9] shown in Tables 5 and 6 in a 100 ml beaker, add 90 g of water, and add caustic soda to dissolve. The pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 5 shows the composition and results of samples in which no rust was generated, and Table 6 shows the compositions and results of samples in which rust was generated.

  The results of Example 3 are shown in Table 5 and Table 6, respectively, and both results are shown together in FIG. As shown in Table 5, when neodecanoic acid or sorbitan monolaurate is used alone, the minimum concentration required to exert a sufficient antirust effect is 1.29% by weight for neodecanoic acid. In the case of sorbitan monolaurate, even when 2.77% by weight was added, no rust preventive effect was shown. As can be seen from FIG. 3, the antirust ability is improved by the combined use of neodecanoic acid and sorbitan monolaurate. Among these, the lower limit concentration at which the sorbitan monolaurate shows a synergistic effect of rust prevention by the addition of sorbitan monolaurate was when sorbitan monolaurate was 34% or more with respect to neodecanoic acid.

  The blending ratio of neodecanoic acid (P) and sorbitan monolaurate (Q) exhibiting a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 4)
Weigh n-octylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and thiodiglycol shown in Tables 7 and 8 in a 100 ml beaker, add 90 g of water, and add caustic soda. Then, the pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 7 shows the composition and results of samples in which rust did not occur, and Table 8 shows the compositions and results of samples in which rust occurred.

  The results of Example 4 are shown in Table 7 and Table 8, and both results are shown together in FIG. As shown in Table 7, when n-octylphosphonic acid or thiodiglycol is used alone, the minimum concentration required to exert a sufficient antirust effect is 1. It was 29% by weight, and even if 1.22% by weight of thiodiglycol was added, no rust preventive effect was shown. As can be seen from FIG. 4, the rust-preventing power is improved by the combined use of n-octylphosphonic acid and thiodiglycol. Of these, the lower limit concentration at which the synergistic effect of rust prevention by adding thiodiglycol was 21% or more with respect to n-octylphosphonic acid.

  The blending ratio of n-octylphosphonic acid (P) and thiodiglycol (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Examples 5-7)
(A) 4 substances of n-hexylthiopropionic acid, (B) neodecanoic acid, (C) n-octylphosphonic acid, and (D) sorbitan monolaurate were each added to a 100 ml beaker so as to have the concentration ratio shown in Table 9. Weighed out, added 90 g of water, added caustic soda to dissolve, adjusted to pH 8.5 ± 0.3, and added water to make 100 g in total. Water was added thereto and diluted every 1.0%, and the rust prevention lower limit concentration was determined according to the evaluation method of rust prevention ability. The results are shown in Table 9 as the rust prevention lower limit concentration at which the rust prevention evaluation is 0.

(Examples 8 to 18)
A test solution in which only one of the compounds (A), (B), (C), and (D) is replaced with another substance so that the concentrations shown in Table 10 are obtained in the same manner as in Examples 5-7. The rust prevention power was evaluated. The substance names replaced are shown in Table 11.

(Comparative Examples 5-9)
From the results of Examples 1, 2, and 3, the results of the lowest total concentration of the two substances are (A) and (C), (C) and (D), and (B) and (D), respectively. Comparative Examples 5, 6 and 7 were used as the lower limit concentrations of the synergistic effect. The concentrations of the blended (A), (B), (C), and (D) are shown in Table 12 in terms of mol / L.

  When the results of Table 9 and Table 12 are compared, the lower limit concentration at which the rust prevention evaluation is “Y” when two types of substances are blended is 0.040 mol / L or 0.060 mol / L. Therefore, the total of the lower limit concentration at which the rust prevention evaluation becomes “Y” when four kinds of substances are blended has been reduced to a maximum of 0.029 mol / L, and the prevention by using three or four kinds of substances together. It shows the synergistic effect of rusting power. When the results of Table 11 and Table 12 are compared, the synergistic effect of the combination of three or four substances is also shown, and the prevention of (A), (B), (C) and (D) is shown. The synergistic effect of rusting power is not limited to these compounds, and it is effective even for substances as shown in Table 11.

(Example 19)
Weigh n-octylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and sorbitan mononeodecanoic acid ester shown in Table 13 and Table 14 in a 100 ml beaker, add 90 g of water, and add caustic soda. Was added and dissolved, the pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 13 shows the composition and results of samples in which rust did not occur, and Table 14 shows the compositions and results of samples in which rust occurred.

  The results of Example 19 are shown in Table 13 and Table 14, respectively, and both results are shown together in FIG. As shown in Table 14, when n-octylphosphonic acid or sorbitan mononeodecanoic acid ester is used alone, the minimum concentration required to exert a sufficient antirust effect is n-octylphosphonic acid, The sorbitan mononeodecanoic acid ester was 1.17% by weight, and even when 1.91% by weight was added, the rust preventive effect was not exhibited. As can be seen from FIG. 5, the rust-preventing power is improved by the combined use of n-octylphosphonic acid and sorbitan mononeodecanoate. Among these, the range which shows a synergistic effect was a case where sorbitan mononeodecanoic acid ester was 40% or more with respect to n-octyl phosphonic acid.

  The blending ratio of n-octylphosphonic acid (P) and sorbitan mononeodecanoic acid ester (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 20)
N-octylphosphonic acid [substitution energy value (erg / cm ² ) =-10.5] and sorbitol tetra n-oleate EO adduct (EO addition mol amount: 30 mol) shown in Table 15 and Table 16. Was weighed into a 100 ml beaker, 90 g of water was added, caustic soda was added and dissolved, the pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 15 shows the composition and results of samples in which no rust was generated, and Table 16 shows the compositions and results of samples in which rust was generated.

  The results of Example 20 are shown in Table 15 and Table 16, respectively. The results of both are shown in FIG. As shown in Table 15, when n-octylphosphonic acid or sorbitol tetra n-oleate EO adduct (30) is used alone, the minimum concentration required to exert a sufficient rust prevention effect is N-octylphosphonic acid was 1.17% by weight, and sorbitol tetra-n-oleate EO adduct (30) did not show a rust preventive effect even when 2.58% by weight was added. As can be seen from FIG. 6, the rust-preventing power is improved by the combined use of n-octylphosphonic acid and sorbitol tetra-n-oleate EO adduct (30). Among these, the range which shows a synergistic effect was a case where sorbitol tetra n-oleate EO adduct (30) is 40% or more with respect to n-octyl phosphonic acid.

  The blending ratio of n-octylphosphonic acid (P) and sorbitol tetra n-oleate EO adduct (30) (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 21)
N-decylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and sorbitan mono n-oleate EO adduct (weight of EO addition: 6 mol) shown in Tables 17 and 18 Was weighed into a 100 ml beaker, 90 g of water was added, caustic soda was added and dissolved, the pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 17 shows the composition and results of samples in which rust did not occur, and Table 18 shows the compositions and results of samples in which rust occurred.

  The results of Example 21 are shown in Table 17 and Table 18, respectively. The results of both are shown in FIG. As shown in Table 17, when n-decylphosphonic acid or sorbitan mono n-oleate EO adduct (6) is used alone, the minimum concentration required to exert a sufficient rust prevention effect is N-decylphosphonic acid was 1.17% by weight, and sorbitan mono n-oleate EO adduct (6) did not show a rust preventive effect even when 1.80% by weight was added. As can be seen from FIG. 7, the rust-preventing power is improved by the combined use of n-decylphosphonic acid and sorbitan mono n-oleate EO adduct (6). Among these, the range which shows a synergistic effect was a case where sorbitan mono n-oleic acid ester EO adduct (6) is 40% or more with respect to n-decylphosphonic acid.

  The blending ratio of n-decylphosphonic acid (P) and sorbitan mono n-oleate EO adduct (6) (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 22)
100 ml of n-octylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and polyglycerin (glycerine mol amount: 6 mol) sesqui-n-undecanoic acid ester of the weight shown in Table 19 and Table 20 Weighed into a beaker, 90 g of water was added, caustic soda was added and dissolved, pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 19 shows the composition and results of samples in which no rust was generated, and Table 20 shows the compositions and results of samples in which rust was generated.

  The results of Example 22 are shown in Table 19 and Table 20, and the results of both are shown together in FIG. As shown in Table 19, when n-octylphosphonic acid or polyglycerin (6) sesqui-n-undecanoic acid ester is used alone, the minimum concentration required to exhibit a sufficient rust prevention effect is n -In octyl phosphonic acid, it was 1.29 weight%, and even if it added 1.60 weight% in polyglycerin (6) sesqui n-undecanoic acid ester, the antirust effect was not shown. As can be seen from FIG. 8, the antirust performance is improved by the combined use of n-octylphosphonic acid and polyglycerin (6) sesqui-n-undecanoic acid ester. Among these, the minimum concentration which shows the synergistic effect of rust prevention by adding polyglycerin (6) sesqui-n-undecanoic acid ester is 40% of polyglycerin (6) sesqui-n-undecanoic acid ester with respect to n-octylphosphonic acid. That was the case.

  The blending ratio of n-octylphosphonic acid (P) and polyglycerin (6) sesqui-n-undecanoic acid ester (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 23)
Weigh n-dodecylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and sorbitan sesqui-n-oleic acid ester shown in Tables 21 and 22 in a 100 ml beaker and add 90 g of water. Then, caustic soda was added and dissolved to adjust the pH to 8.5 ± 0.3, and water was further added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 21 shows the composition and results of samples in which rust did not occur, and Table 22 shows the compositions and results of samples in which rust occurred.

  The results of Example 23 are shown in Table 21 and Table 22, and the results of both are shown together in FIG. As shown in Table 21, when n-dodecylphosphonic acid or sorbitan sesqui n-oleate is used alone, the minimum concentration required to exert a sufficient rust prevention effect is n-dodecylphosphonic acid. In the case of sorbitan sesqui-n-oleic acid ester, 1.60% by weight was added, and no rust preventive effect was exhibited. As can be seen from FIG. 9, the rust-preventing power is improved by the combined use of n-dodecylphosphonic acid and sorbitan sesqui-n-oleic acid ester. Among these, the lower limit concentration which shows the synergistic effect of rust prevention by addition of sorbitan sesqui-n-oleic acid ester was when sorbitan sesqui-n-oleic acid ester was 40% or more with respect to n-dodecylphosphonic acid.

  The blending ratio of n-dodecylphosphonic acid (P) and sorbitan sesqui n-oleic acid ester (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 24)
Weigh phenylphosphonic acid and sorbitan monolaurate in the weight shown in Table 23 and Table 24 in a 100 ml beaker, add 90 g of water, add caustic soda to dissolve, and adjust the pH to 8.5 ± 0.3. Further, water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 23 shows the composition and results of samples in which rust did not occur, and Table 24 shows the compositions and results of samples in which rust occurred.

  The results of Example 24 are shown in Table 23 and Table 24, and both results are shown together in FIG. As shown in Table 23, when phenylphosphonic acid or sorbitan monolaurate is used alone, the minimum concentration required to exert a sufficient antirust effect is 1.58% by weight for phenylphosphonic acid. Even when added, sorbitan monolaurate did not show rust prevention effect even when 2.00% by weight was added. As can be seen from FIG. 10, the rust-preventing power is improved by the combined use of phenylphosphonic acid and sorbitan monolaurate.

  The blending ratio of phenylphosphonic acid (P) and sorbitan monolaurate (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 25)
Weigh n-octylphosphonic acid [substitution energy value (erg / cm ² ) = − 10.5] and n-heptylthioglycerol shown in Table 25 and Table 26 in a 100 ml beaker, add 90 g of water, Caustic soda was added and dissolved to adjust the pH to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 25 shows the composition and results of samples in which no rust was generated, and Table 26 shows the compositions and results of samples in which rust was generated.

  The results of Example 25 are shown in Table 25 and Table 26, and both results are shown together in FIG. As shown in Table 25, when n-octylphosphonic acid or n-heptylthioglycerol is used alone, the minimum concentration required to exert a sufficient antirust effect is n-octylphosphonic acid, It was 0.97% by weight, and n-heptylthioglycerol showed no rust preventive effect even when 1.86% by weight was added. As can be seen from FIG. 11, the antirust ability is improved by the combined use of n-octylphosphonic acid and n-heptylthioglycerol. Among these, the lower limit concentration at which the synergistic effect of rust prevention by adding n-heptylthioglycerol was 27% or more with respect to n-octylphosphonic acid was n-heptylthioglycerol.

  The blending ratio of n-octylphosphonic acid (P) and n-heptylthioglycerol (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 26)
Weigh oleic acid and sorbitan monolaurate shown in Table 27 and Table 28 into a 100 ml beaker, add 90 g of water, add caustic soda to dissolve, adjust the pH to 8.5 ± 0.3, Water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 27 shows the composition and results of samples in which rust was not generated, and Table 28 shows the compositions and results of samples in which rust was generated.

  The results of Example 26 are shown in Table 27 and Table 28, respectively. The results of both are shown in FIG. As shown in Table 27, when oleic acid or sorbitan monolaurate is used alone, the minimum concentration required to exert a sufficient rust prevention effect is 1.98% by weight for oleic acid. In addition, sorbitan monolaurate did not show rust preventive effect even when added at 2.00% by weight. As can be seen from FIG. 12, the rust-preventing power is improved by the combined use of oleic acid and sorbitan monolaurate. Among these, the range which shows a synergistic effect was a case where sorbitan monolaurate is 9% or more with respect to oleic acid.

  The blending ratio of oleic acid (P) and sorbitan monolaurate (Q) exhibiting a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 27)
Weigh neodecanoic acid and sorbitan monooleate shown in Table 29 and Table 30 in a 100 ml beaker, add 90 g of water, add caustic soda to dissolve, adjust the pH to 8.5 ± 0.3, Was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 29 shows the composition and results of samples in which rust was not generated, and Table 30 shows the compositions and results of samples in which rust was generated.

  The results of Example 27 are shown in Table 29 and Table 30, respectively. The results of both are shown in FIG. As shown in Table 29, when neodecanoic acid or sorbitan monooleate is used alone, the minimum concentration required to exert a sufficient antirust effect is 1.29% by weight for neodecanoic acid, In the case of sorbitan monooleate, even when 2.00% by weight was added, no rust preventive effect was shown. As can be seen from FIG. 13, the antirust ability is improved by the combined use of neodecanoic acid and sorbitan monooleate. Among these, the range which shows a synergistic effect was a case where sorbitan monooleate is 20% or more with respect to neodecanoic acid.

  The blending ratio of neodecanoic acid (P) and sorbitan monooleate (Q), which shows a strong synergistic effect, is expressed by the following formula, and a graph is shown in FIG.

(Example 28)
Weigh p-tertbutylbenzoic acid and sorbitan monooleate in the weights shown in Table 31 and Table 32 into a 100 ml beaker, add 90 g of water, dissolve with caustic soda, and adjust the pH to 8.5 ± 0.3. Further, water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 31 shows the composition and results of samples in which rust did not occur, and Table 32 shows the compositions and results of samples in which rust occurred.

  The results of Example 28 are shown in Table 31 and Table 32, respectively. The results of both are shown in FIG. As shown in Table 31, when p-tertbutylbenzoic acid or sorbitan monooleate is used alone, the minimum concentration required to exert a sufficient anticorrosive effect is p-tertbutylbenzoic acid, It was 1.78% by weight, and sorbitan monooleate did not show a rust preventive effect even when 2.00% by weight was added. As can be seen from FIG. 14, the anticorrosive ability is improved by the combined use of p-tertbutylbenzoic acid and sorbitan monooleate. Among these, the range which shows a synergistic effect was a case where sorbitan monooleate is 16% or more with respect to p-tert butylbenzoic acid.

  The blending ratio of p-tert-butylbenzoic acid (P) and sorbitan monooleate (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Examples 29 to 33)
In order to investigate the synergistic effect of rust-preventing power when combining three or more substances, the three substances of neodecanoic acid, n-octylphosphonic acid and water-substituted surfactant are adjusted to the concentration ratios shown in Table 33. Weighed into a 100 ml beaker, added 90 g of water, added caustic soda to dissolve, adjusted to pH 8.5 ± 0.3, and further added water to make 100 g in total. Water was added thereto and diluted every 1.0%, and the rust prevention lower limit concentration was determined according to the evaluation method of rust prevention ability. The results are shown in Table 33 as the rust prevention lower limit concentration at which the rust prevention evaluation is “Y”.

(Example 34)
The weight of 3- (2-benzothiazolylthio) propionic acid and sorbitan monolaurate shown in Table 34 and Table 35 is weighed into a 100 ml beaker, 90 g of water is added, and caustic soda is added to dissolve, and the pH is adjusted to 8. The total amount was adjusted to 5 ± 0.3, and water was further added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 34 shows the composition and results of samples in which rust did not occur, and Table 35 shows the compositions and results of samples in which rust occurred.

  The results of Example 34 are shown in Table 34 and Table 35, respectively. The results of both are shown in FIG. As shown in Table 34, when 3- (2-benzothiazolylthio) propionic acid or sorbitan monolaurate is used alone, the minimum concentration required to exhibit a sufficient rust prevention effect is 3 In-(2-benzothiazolylthio) propionic acid, it was 1.68% by weight, and in sorbitan monolaurate, even when 2.00% by weight was added, no rust preventive effect was shown. As can be seen from FIG. 15, the rust prevention power is improved by the combined use of 3- (2-benzothiazolylthio) propionic acid and sorbitan monolaurate. Among these, the range which shows a synergistic effect was a case where sorbitan monolaurate is 11% or more with respect to 3- (2-benzothiazolylthio) propionic acid.

  The blending ratio of 3- (2-benzothiazolylthio) propionic acid (P) and sorbitan monolaurate (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 35)
The weights of 3- (2-benzothiazolylthio) acetic acid and sorbitan monooleate shown in Table 36 and Table 37 are weighed into a 100 ml beaker, 90 g of water is added, caustic soda is added and dissolved, and the pH is adjusted to 8.5 ±. The total amount was adjusted to 0.3, and water was further added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 36 shows the composition and results of samples in which rust did not occur, and Table 37 shows the compositions and results of samples in which rust occurred.

  The results of Example 35 are shown in Table 36 and Table 37, respectively. The results of both are shown in FIG. As shown in Table 36, when 3- (2-benzothiazolylthio) acetic acid or sorbitan monooleate is used alone, the minimum concentration required to exert a sufficient rust prevention effect is 3- ( In 2-benzothiazolylthio) acetic acid, it was 1.58% by weight, and in sorbitan monooleate, even when 2.00% by weight was added, no rust preventive effect was shown. As can be seen from FIG. 16, the rust prevention power is improved by the combined use of 3- (2-benzothiazolylthio) acetic acid and sorbitan monooleate. Among these, the range which shows a synergistic effect was a case where sorbitan monolaurate is 23% or more with respect to 3- (2-benzothiazolylthio) acetic acid.

  The blending ratio of 3- (2-benzothiazolylthio) acetic acid (P) and sorbitan monooleate (Q), which shows a strong synergistic effect, is expressed by the following formula, and a graph is shown in FIG.

(Example 36)
3- (2-Benzothiazolylthio) propionic acid and n-tetradecylphosphonic acid of the weight shown in Table 38 and Table 39 are weighed into a 100 ml beaker, 10 g of propylene glycol and 80 g of water are added, and caustic soda is added to dissolve. The pH was adjusted to 8.5 ± 0.3, and water was added to make the total amount 100 g. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 38 shows the composition and results of samples in which rust did not occur, and Table 39 shows the compositions and results of samples in which rust occurred.

  The results of Example 36 are shown in Table 38 and Table 39, respectively. The results of both are shown in FIG. As shown in Table 38, when 3- (2-benzothiazolylthio) propionic acid or n-tetradecylphosphonic acid is used alone, the minimum concentration required to exert a sufficient rust prevention effect is In 3- (2-benzothiazolylthio) propionic acid, it was 1.68% by weight, and in n-tetradecylphosphonic acid, it was 1.58% by weight. As can be seen from FIG. 17, the rust-preventing power is improved by the combined use of 3- (2-benzothiazolylthio) propionic acid and n-tetradecylphosphonic acid. Among these, the range which shows a synergistic effect was a case where n-tetradecyl phosphonic acid was 22% or more with respect to 3- (2-benzothiazolylthio) propionic acid.

  The blending ratio of 3- (2-benzothiazolylthio) propionic acid (P) and n-tetradecylphosphonic acid (Q) showing a strong synergistic effect is represented by the following formula, and a graph is shown in FIG.

(Example 37)
The weights of n-hexylthiohexanoic acid and n-octylphosphonic acid shown in Tables 40 and 41 are weighed into a 100 ml beaker, 90 g of water is added, caustic soda is added and dissolved, and the pH is 8.5 ± 0.3. The total amount was adjusted to 100 g by adding water. This was used as a test solution, and the antirust ability was evaluated according to the above-described antirust ability evaluation method. Table 40 shows the composition and results of samples in which rust did not occur, and Table 41 shows the compositions and results of samples in which rust occurred.

  The results of Example 37 are shown in Table 40 and Table 41, respectively. The results of both are shown in FIG. As shown in Table 40, when n-hexylthiohexanoic acid or n-octylphosphonic acid is used alone, the minimum concentration required to exert a sufficient antirust effect is n-hexylthiohexanoic acid. In the case of n-octylphosphonic acid, it was 1.16% by weight. As can be seen from FIG. 18, the antirust ability is improved by the combined use of n-hexylthiohexanoic acid and n-octylphosphonic acid. Among these, the range which shows a synergistic effect was a case where n-octyl phosphonic acid was 13% or more with respect to n-hexyl thiohexanoic acid.

  The blending ratio of n-hexylthiohexanoic acid (P) and n-octylphosphonic acid (Q), which shows a strong synergistic effect, is expressed by the following formula, and a graph is shown in FIG.

Claims (11)

(i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) A metal corrosion inhibitor composition comprising 2, 3, or 4 selected from at least one of a sulfur-containing compound or a salt thereof. The surfactant is
The following formula (1)
D _WO = γ _SO −γ _SW = γ _WO cos θ (1)
D _WO : substitution energy, γ _SO : metal / oil surface tension, γ _SW : metal / water surface tension,
gamma _WO: surface tension between water / oil, theta: receding contact angle, each of the surface tension is a surfactant having a negative value of replacement energy D _WO represented by measured at 25 ° C., to claim 1 The metal corrosion inhibitor composition as described.   The metal corrosion inhibitor composition according to claim 1 or 2, wherein the surfactant is a sorbitan esterified product, a sorbitol esterified product or a polyglycerol esterified product.   The metal corrosion inhibitor composition according to any one of claims 1 to 3, wherein the organic acid having 4 or more carbon atoms is a carboxylic acid having 4 or more carbon atoms.   The metal corrosion inhibitor composition according to claim 4, wherein the carboxylic acid having 4 or more carbon atoms is a carboxylic acid having 4 to 15 carbon atoms. The phosphorus-containing compound is represented by the following general formula (2):

[However, R ¹ represents a linear or branched alkyl group having 2 to 15 carbon atoms which may have an aryl group.
l represents an integer of 0-20.
When l is 1, R ² represents a bond or a linear or branched alkylene group having 1 to 4 carbon atoms.
When l is 2 to 20, R ² represents a linear or branched alkylene group having 2 to 4 carbon atoms. ]
The metal corrosion inhibitor composition according to any one of claims 1 to 5, which is a compound represented by the formula: The sulfur-containing compound has the following general formula (3):

[In Formula (3), Y is the following formula (y1) optionally substituted with a sulfur atom or a hydroxyl group:

The group represented by these is shown.
m shows 1-3.
R ^a is a hydroxyl group or the following general formula (a);

(In the general formula (a), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom; an alkyl group optionally substituted with a hydroxyl group; or an aryl group optionally substituted with a hydroxyl group.
Here, R ⁴ and R ⁵ may form a carbonyl group together with the carbon atoms to which they are bonded. )
The group represented by these is shown.
R ³ represents a bond; an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; an arylene group which may be substituted with a hydroxyl group or a carboxyl group A monoether group optionally substituted with a hydroxyl group or a carboxyl group; or a polyether optionally substituted with a hydroxyl group or a carboxyl group.
R ^b represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group or a carboxyl group; an aryl group which may be substituted with a hydroxyl group or a carboxyl group; or the following general formula (b):

(In the formula (b), R ⁶ is an alkylene group which may be substituted with a hydroxyl group or a carboxyl group; an alkenylene group which may be substituted with a hydroxyl group or a carboxyl group; a substituent which is substituted with a hydroxyl group or a carboxyl group. An arylene group which may be substituted; a monoether group which may be substituted with a hydroxyl group or a carboxyl group; or a polyether group which may be substituted with a hydroxyl group or a carboxyl group.
R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom; an alkyl group which may be substituted with a hydroxyl group; or an aryl group which may be substituted with a hydroxyl group.
Here, R ⁷ and R ⁸ may form a carbonyl group together with the carbon atoms to which they are bonded. )
The group represented by these is shown.
However, when ^Rb represents a hydrogen atom, Y represents a group represented by the formula (y1). ]
The metal corrosion inhibitor composition as described in any one of Claims 1-6 which is a compound represented by these.   Sulfur-containing compounds are 2-benzothiazolylthioacetic acid, 4-methyl-2-benzothiazolylthioacetic acid, 6-amino-2-benzothiazolylthioacetic acid, 3- (2-benzothiazolylthio) -propionic acid 3- (4-Methyl-2-benzothiazolylthio) -propionic acid, 3- (6-amino-2-benzothiazolylthio) -propionic acid, 3- (4,6-dimethyl-2-benzothia Zolylthio) -propionic acid, 2- (2-benzothiazolylthio) -propionic acid, 2- (4-methyl-2-benzothiazolylthio) -propionic acid, 5- (2-benzothiazolylthio)- Valeric acid, 3- (2-benzothiazolylthio) valeric acid, 5- (4-methyl-2-benzothiazolylthio) -valeric acid, 3- (2-benzothiazolylthio) -acrylic acid, 3- (4-me Ru-2-benzothiazolylthio) -propionic acid, 4- (2-benzothiazolylthio) -butyric acid, 4- (4-methyl-2-benzothiazolylthio) -butyric acid, 4- (6-amino- The compound is selected from the group consisting of 2-benzothiazolylthio) -butyric acid, 2- (2-benzothiazolylthio) -benzoic acid, 2- (4-methyl-2-benzothiazolylthio) -benzoic acid. Metal corrosion inhibitor composition in any one of 1-7. (i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) The metal corrosion inhibitor composition according to any one of Items 1 to 8, comprising 3 or 4 selected from at least one of a sulfur-containing compound or a salt thereof. (i) at least one of a surfactant or a salt thereof;
(ii) at least one of an organic acid having 4 or more carbon atoms or a salt thereof;
(iii) at least one of a phosphorus-containing compound or a salt thereof; and
(iv) The metal corrosion inhibitor composition according to any one of Items 1 to 9, wherein the composition contains at least one of at least one of a sulfur-containing compound or a salt thereof. The metal corrosion prevention method characterized by processing a metal using the metal corrosion inhibitor composition as described in any one of Claims 1-10.

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