JPH07794B2 - anti-rust - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a rust preventive agent for aluminum.

[Conventional technology]

Heretofore, as a rust preventive agent for aluminum and aluminum alloys, alkyl phosphoric acid ester, aliphatic carboxylic acid ester, aliphatic carboxylic acid amine salt, aromatic carboxylic acid salt, fatty acid amide and the like have been known.

[Problems to be solved by the invention]

However, these materials do not fully satisfy the user in terms of rust prevention of aluminum and aluminum alloy processing. That is, when these compounds are used by adding them to rolling oil and cutting oil for aluminum and aluminum alloy processing, stains such as water stain and oil stain cannot be sufficiently suppressed.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of extensive studies on rust preventive agents capable of preventing rust such as water stains and oil stains generated on the surfaces of aluminum and aluminum alloys. That is, the present invention relates to a phosphoric acid partial ester (salt) of an oxyalkylated amine (a) or a hydroxyalkylamine (hydroxyalkyl having 5 or more carbon atoms) represented by the following general formula (1) (b). A) an anticorrosive for aluminum (first invention), and an oxyalkylated amine (a) or a hydroxyalkylamine (wherein the hydroxyalkyl has 5 or more carbon atoms) (b) A rust preventive agent for aluminum (second invention), which comprises a phosphoric acid partial ester (salt) (A) and an alkanolamine (B).

In the present invention, the oxyalcarized amine (a) has the general formula [In the formula, R ₁ is an organic group having a hydrocarbon group of C ₄ or more; R ₂ is H, an organic group having a hydrocarbon group or A ₂ On ₂ H, and R ₁ and R ₂ are oxygen atoms in some cases. Alternatively, they may be linked to each other via a nitrogen atom to form a 5- to 7-membered ring with N. A ₁ and A ₂ are C _{2 to} C ₄ alkylene groups; n ₁ and n ₂ are integers of 1 or more.] Are used.

R ₁ in the general formula (1) is an organic group having a C ₄ or higher hydrocarbon group, an organic group having a C ₄ or more hydrocarbon groups and C ₄ and higher hydrocarbons group. As the C ₄ or more hydrocarbon group, an aliphatic hydrocarbon group such as C ₄ to ₂₂ , preferably C ₈ to ₁₈ alkyl group or alkenyl group (butyl group, hexyl group, 2-ethylhexyl group, octyl group,
Dodecyl group, stearyl group, oleyl group, etc.); cycloalkyl group (cyclohexyl group, etc.) and aromatic hydrocarbon group (phenyl group, naphthyl group, etc. aryl group;
Aralkyl groups such as benzyl group; alkaryl groups such as butylphenyl group).

Further, examples of the organic group having a hydrocarbon group of C ₄ or more include the following groups.

1) Hydrocarbon group containing amino group 2) Hydrocarbon group containing amide group 3) ester group-containing hydrocarbon group _{R '1 COOA' 2 (3} ') 4) ether group-containing hydrocarbon group _{R' 1 OA '2 (4} ') wherein, R _'1 is C ₄ and higher hydrocarbons group; a _'1 is an alkylene group of C ₂ ~ _{6; a'} alkylene group of ₂ C ₂ ~ _4; X is H, C ₄
More is a hydrocarbon group or A _'4 On' ₁ H. In the general formulas (1 ′) to (4 ′), A ′ ₄ is A ₁ and; n ′ ₁ is n ₁ , n ₂ and R ′ ₁ and R ′ _{1 in the} general formula (1).
C ₄ or more hydrocarbon groups are respectively C ₄ or higher hydrocarbon group in R ₁ described above the same group.

A _'1 is an alkylene group of C ₂ ~ _6, ethylene, propylene and hexamethylene group. A _'2 is
An alkylene group of C ₂ ~ _4, is the same group as A _1.

Among R ₁ in the general formula (1), preferred is a C ₄ or more hydrocarbon group, and particularly preferred is an alkyl group.

R ₂ is H, an organic group having a hydrocarbon group or A ₂ O) n ₂ H. As the organic group having a hydrocarbon group, C ₁ or more,
Preferably an organic group having a hydrocarbon group or a hydrocarbon group of C ₁ ~ _22. These can be quoted as they are, except that C ₄ or more is changed to C ₁ or more in R ₁ .

R ₁ and R ₂ are optionally connected to each other via an oxygen atom or a nitrogen atom to form a divalent organic group having 4 to 6 carbon atoms, for example,
CH ₂ m ′ (m ′ is 4 to 6), —CH ₂ CH ₂ OCH ₂ CH ₂ — and (R _'2 is H or an alkyl group C ₁ ~ ₄₎ to form,
It may form a 5- to 7-membered ring with N, and examples of the cyclic group include a piperidino group, a morpholino group and a piperazino group.

A _1, A ₂ is an alkylene group of C ₂ ~ _4, an ethylene group, a propylene group, a butylene group and ethylene, propylene combination system (random, block) and the like. Preferred are an ethylene group, a propylene group and a combination system thereof (random, block).

n ₁ and n ₂ are integers of 1 or more, preferably 1 to 20. The total number of n (the total number of moles of alkylene oxide added, n ₁ + n ₂ + n ′ _1, ...) Is usually 1 or more, preferably 1 to 20, particularly preferably 1 to 10. the sum of n
If it is more than 20, the rust preventive property is likely to deteriorate.

In the present invention, the oxyalkylated product (b) of hydroxyalkylamine (hydroxyalkyl having 5 or more carbon atoms: hereinafter referred to as hydroxyalkylamine) has the general formula (In the formula, R ₃ is a C ₃ or more aliphatic hydrocarbon group; R ₄ , R ₅ , and R ₆
Is H, an organic group having a hydrocarbon group, or A ₃ O) n ₃ H, R ₇ is H or A ₃ On ₃ H, and R ₄ , R ₅ , R ₆ , and R _{7 are}
At least one of them is A ₃ O) n ₃ H. R ₄ and R ₅ may be optionally connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring with N. A is an alkylene group and m is 0 or an integer of 1 to 6. A ₃ is C ₂ ~ ₄
Alkylene group; n ₃ is an integer of 1 or more. ] The compound shown by these is mentioned.

R ₃ is a C ₃ or more aliphatic hydrocarbon group, for example, C ₃ ~
₂₂ is preferably an alkyl or alkenyl group of C ₈ ~ ₁₈ (butyl group, a hexyl group, a 2-ethylhexyl group, octyl group, dodecyl group, stearyl group, oleyl group); and (cyclohexyl group) cycloalkyl group mentioned To be If R ₃ is C ₂ or less (or the carbon number of the hydroxyalkyl group is 4 or less), the rust preventive power is lowered. R ₃
Of these, preferred is an alkyl group.

R ₄ , R ₅ and R ₆ are H, an organic group having a hydrocarbon group, or
A ₃ O) n ₃ H, R ₇ is H or A ₃ On ₃ H, R ₄ ,
At least one of R ₅ , R ₆ and R ₇ is A ₃ O) n ₃ H.
Examples of the organic group having a hydrocarbon group in R ₄ , R ₅ , R ₆ and R ₇ include a hydrocarbon group having C ₁ or more, preferably C ₁ to ₂₂ or an organic group having this hydrocarbon group. They are
In R ₁ , the description can be cited as it is, except that C ₄ or more is changed to C ₁ or more, and an alkyl group is preferable.

R ₄ and R ₅ are optionally connected to each other via an oxygen atom or a nitrogen atom to form a divalent organic group having 4 to 6 carbon atoms, for example,
CH ₂ m ′ (m ′ is 4 to 6), —CH ₂ CH ₂ OCH ₂ CH ₂ — and (R _'2 is H or an alkyl group C ₁ ~ ₄₎ to form,
A 5- to 7-membered ring may be formed with N, and examples of the cyclic group include a piperazino group, a morpholino group and a piperazino group.

A is an alkylene group such as ethylene of C ₂ ~ ₆ alkylene group, propylene, hexamethylene group. Ethylene groups and propylene groups are preferred. A ₃ is an alkylene group of C ₂ ~ _4, an ethylene group, Piropiren group, butylene group and ethylene, propylene combination system (random, block) and the like. Preferred are an ethylene group, a propylene group and a combination system thereof (random, block). m is 0 or an integer of 1 to 6,
It is preferably 0 or 1. n ₃ is an integer of 1 or more, preferably an integer of 1-20. The _{R 4, R 5, R 6} , the R ₇ at least one (A ₃ O) n ₃ 1 pieces included in the H or a plurality of n ₃
Is usually 1 or more, preferably 1 to 20, particularly preferably 1 to 10. If the total is more than 20, the rust preventive property tends to decrease.

As a partial ester of phosphoric acid of an oxyalkylated amine (a) or an oxyalkylated compound (b) of a hydroxyalkylamine (hydroxyalkyl having 5 or more carbon atoms), a general formula [In the formula, Q is a residue of an oxyalkylated amine (a) or an oxyalkylated product of a hydroxyalkylamine (b). 1 is an integer of 1 or more, q is an integer of 1 to 1, a is 1 or 2, M is H, an alkali metal, ammonium or an amine cation. ] The compound shown by these is mentioned.

In the general formula (4) or (5), Q represents a residue,
An oxyalkylated amine (a) or a hydroxyalkylamine oxyalkylated product (b) from which an OH group has been removed. l is an integer of 1 or more and is usually 1 to 9, preferably 1 to 5. Li, Na, K as the alkali metal of M
And the like; examples of amine cations include alkyl or alkenylamines (methylamine, dimethylamine, ethylamine, diethylamine, propylamine, etc.); alkanolamines (alkanolamines include later-described alicanolamines (B)). ) And other amine cations. Preferred among M are alkanolamines.

Oxyalkylated amine (a) or hydroxyalkylamine (hydroxyalkyl has 5 or more carbon atoms)
Examples of the ester (salt) of the phosphoric acid moiety of the oxyalkylated product (b) are shown below. In the following description, dieta represents diethanolamine, monoethane represents monoethanolamine, EO represents ethylene oxide, PO represents propylene oxide, and, for example, (P
O) ₆ represents a PO6 mole adduct and uses the same notation.

(1) Phosphoric acid partial ester (salt) of oxyalkylated aliphatic amine Octylamine (PO) ₂ phosphoric acid partial ester diet salt,
Lauryl amine (EO) ₄ phosphoric acid partial ester mono-etha salt, lauryl amine (EO) ₂ phosphoric acid partial ester Na salt,
Laurylamine (PO) ₂ (FO) ₄ Phosphoric Acid Partial Ester Monoetha Salt, N-Methyllaurylamine (EO) ₆ Phosphoric Acid Partial Ester Dieter Salt, Laurylamine (PO) ₈ Phosphate Partial Ester Monoester, Stearylamine ( EO) ₄ phosphoric acid partial ester Na salt, stearyl propylene diamine (EO) ₁₀ phosphoric acid partial ester monoetha salt, etc. (2) Phosphoric acid partial ester (salt) of hydroxyalkyl amine hydroxyalkylamine 2-hydroxyoctylamine (PO ) ₂ phosphate partial ester mono ethanolate salt, 2-hydroxy-decyl amine _{(EO) 4}
Phosphoric acid partial ester / dieta salt, 2-hydroxypalmitylamine (EO) ₆ phosphoric acid partial ester / monoeta salt,
N, N-Dimethyl-2-hydroxylaurylamine (EO)
_2- phosphate partial ester Na salt, N, N-dimethyl-2-hydroxypalmityl (PO) ₄ -phosphate partial ester monoetha salt, N, N-diethyl-2-hydroxypalmityl (E
O) _6- phosphate partial ester diet salt, N, N-dimethyl-2
-Hydroxystearylamine (EO) _4- phosphoric acid partial ester, diethyl salt, etc. (3) Oxyalkylated aromatic amines Phosphoric acid partial ester (salt) Aniline (EO) _4- phosphoric acid partial ester Na salt, aniline (PO) _6- phosphoric acid Partial ester diet salt, benzylamine (PO) ₄ phosphate partial ester monoetha salt, etc. (4) Phosphoric acid partial ester (salt) of oxyalkylated alicyclic or heterocyclic amine morpholine (EO) ₂ phosphate partial ester monoester salt , Cyclohexylamine (EO) ₄ phosphoric acid partial ester monoether salt, etc. The partial ester (salt) in the present invention can be produced by a known method. For example, a catalyst for amine compounds (NaO
H, KOH, etc.), usually at 50 to 200 ° C., alkylene oxides such as ethylene oxide and propylene oxide are added individually or by mixing two or more kinds individually or as a mixture, and amine oxyalkylene ether is added to form a terminal hydroxyl group. Esterification with phosphoric anhydride (or phosphoric acid) such that at least one active hydrogen remains. When phosphoric anhydride is used in this reaction, it is usually heated to 30 to 100 ° C. and the reaction proceeds easily without using a catalyst. When phosphoric acid is used, it can usually be dehydrated at 100 to 200 ° C for esterification. After esterification, the active hydrogen part of the phosphoric acid partial ester should be neutralized with an alkaline substance (alkali metal hydroxide, carbonate; alkaline earth metal hydroxide; ammonia; amine) by a known method to obtain a salt. You can

The rust preventive agent of the present invention may contain a phosphoric acid partial ester (salt) of an oxyalkylated amine (a) or an oxyalkylated product (b) of a hydroxyalkylamine, but when it further contains an alkanolamine. Further, there is an effect that the rust preventive power is improved. The alkanolamines (B) used in the present invention have the general formula [In the formula, R ₈ and R ₉ are H, a hydrocarbon group or A ₅ O) n ₅ H, n ₄ and n ₅ are integers of 1 or more, and A ₄ and A ₅ are C ₂ to C ₄ alkylene groups. Is. R ₈ and R ₉ may optionally be linked to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring with N].

The hydrocarbon group represented by R ₈ and R ₉ in the general formula (3) is an aliphatic hydrocarbon group such as a C ₁ to ₂₂ , preferably a C ₈ to ₂₀ alkyl group or alkenyl group (methyl group, ethyl group, propyl group). , Butyl group, octyl group, lauryl group, stearyl group, oleyl group) and cycloalkyl group (cyclohexyl group).

R ₈ and R ₉ are optionally connected to each other via an oxygen atom or a nitrogen atom to form a divalent organic group having 4 to 6 carbon atoms, for example,
CH ₂ m ′ (m ′ is 4 to 6), —CH ₂ CH ₂ OCH ₂ CH ₂ — and (R _'2 is H or an alkyl group C ₁ ~ ₄₎ to form,
It may form a 5- to 7-membered ring with N, and examples of the cyclic group include a piperidino group, a morpholino group and a piperazino group.

The alkylene group of C ₂ ~ ₄ of A _4, A ₅ ethylene, propylene and butylene group. n ₄ and n ₅ are integers of 1 or more, preferably 1 to 6.

Specifically, as alkanolamines, usual alkanolamines (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine,
Butanolamine, etc.), alicyclic amine alkylene oxide adduct (cyclohexylaminoethanol, cyclohexylamine alkylene oxide adduct, etc.),
Aliphatic amine alkylene oxide adducts (octylamine, laurylamine, palmitylamine, stearylamine, alkylene oxide adducts such as diethylaminoethanol etc.), and heterocyclic amine alkylene oxide adducts (monophorine alkylene oxide adduct etc.) can give. Preferred among these are monoethanolamine, diethanolamine, triethanolamine and cyclohexylaminoethanol.

The weight ratio of (A) and (B) is usually 99.5: 0.5 to 50: 5.
It is 0, preferably 95: 5 to 70:30. If the amount of (B) is less than 0.5, the effect of adding (B) is particularly low, and if the amount of (B) is more than 50, the anticorrosive property is deteriorated.

The method of mixing (A) and (B) is not particularly limited. For example, a method of dissolving (B) in water and then adding (A) and mixing and stirring; (A) and (B) in water. To the
A method of mixing and stirring can be mentioned. The former is preferred. Mixing may be at room temperature or warming. Further, when the cation used for the neutralization of (A) is an alkanolamine, an excess amount of the alkanolamine is added during the neutralization to form a mixture of the neutralization salt (A) and the alkanolamine (B). Good.

The rust preventive agent of the present invention comprises the component (A), the component (A) and the component (B).
However, if necessary, an antifoaming agent, a surfactant and the like can be added within a range that does not reduce the effect.

Examples of aluminum to which the rust preventive agent of the present invention is applied include aluminum and aluminum alloys. Aluminum alloys for casting (Al-Cu system, Al-Cu-Si
System, Al-Si system, Al-Cu-Mg-Ni system, Al-Mg system alloy, etc.)
And processing alloys (high strength aluminum alloys such as Al-
Cu-based, Al-Cu-Mg-based, Al-Zn-Mg-based, Al-Cu-Ni-based and Al-Si-based alloys, corrosion resistant alloys such as Al-Mg-based, Al-Mn
And Al-Mg ² Si-based alloys).

Examples of the shapes of aluminum and aluminum alloys include plastic processed products such as plates, pipes and bars, and machined parts such as machines and automobiles. As the method of using the rust preventive agent for aluminum, plastic processed products such as plates, pipes and rods and machined parts such as machines and automobiles are subjected to rust preventive treatment by dipping or spraying in an aqueous solution and mineral oil diluted with the rust preventive agent of the present invention. To do. The concentration of the rust preventive agent to be diluted is usually 0.2 to 10% by weight, preferably 0.5 to 5% by weight. Furthermore, the rust preventive agent of the present invention can be used by adding it to processing oils such as rolling oil, cutting oil and press oil. In that case, the addition amount of the rust preventive agent is 1 to 30% by weight, preferably 1 to 10%.
% By weight.

〔Example〕

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 11 and Comparative Examples 1 to 5 Rust preventive agent of the present invention Example 1 Octylamine (PO) ₂ phosphate partial ester diethanolamine salt Example 2 Laurylamine (EO) ₂ phosphate partial ester Na salt Example 3 Laurylamine (EO) ₄ phosphate partial ester monoethanolamine salt Example 4 Laurylamine (PO) ₆ phosphate partial ester monoethanolamine salt Example 5 Stearylamine (EO) ₆ phosphate partial ester monoethanolamine salt Example 6 2-hydroxylaurylamine (EO) ₆ phosphoric acid partial ester monoethanolamine salt Example 7 2-hydroxypalmitylamine (EO) ₄ phosphoric acid partial ester Na salt Example 8 2-hydroxypalmitylamine (PO) ₂ (EO) ₆ phosphate partial ester diethanolamine salt example 9 2-hydroxy-stearylamine EO) ₈ phosphoric acid partial ester Na salt Example 10 N, N-dimethyl-2-hydroxy-laurylamine (EO)
_4- Phosphoric acid partial ester monoethanolamine salt Example 11 N, N-diethyl-2-hydroxypalmitylamine (E
O) ₄ Phosphoric acid partial ester diethanolamine salt Comparative rust inhibitor Comparative example 1 Nitrite-amine rust inhibitor Comparative example 2 Benzoic acid / diethanolamine salt Comparative example 3 Oleic acid / diethanolamine salt Comparative example 4 Lauric acid alkanolamide Comparative example 5 Various performances of laurylamine (EO) ₆ were evaluated by the following test methods. The test pieces used in the test were obtained by immersing JIS A 1050P in a test solution of a 1% aqueous solution of a rust preventive agent for a wet pack test and a spot test, and dropping it. For the immersion test, the test solution was immersed in a 0.5% aqueous solution of a rust preventive agent.

Various performances of the rust preventive agent of the present invention (Examples 1 to 11) and the following rust preventive agent comparative products (Comparative Examples 1 to 5) were evaluated. The grayish brown and white rusty water stains were evaluated by a wet pack test, and the brownish brown oil stains were evaluated by a spot test. The results are shown in Table-1.

(1) Wet pack test Aluminum plate immersed in test solution (100 x 50 x 1.2
(mm) were superposed on each other, and the stainless steel plates were sandwiched between the top and bottom, and the four corners were tightened with bolts.

This was left for 1 day in a thermo-hygrostat having a humidity of 90% and a temperature of 50 ° C., and the state of rust on the overlapping portions of the aluminum plates was observed.

(2) Immersion test Immerse an aluminum plate (70 x 12 x 2 mm) in the test solution,
It was left for 2 days at room temperature and observed in the state of rust and discoloration.

(3) Spot test Titrate the test solution on an aluminum plate (30 x 30 x 1.2 mm), and after air drying, leave it in a thermo-hygrostat at a humidity of 90% and a temperature of 50 ° C for 3 days to observe rust and discoloration. did.

Example 12 Anticorrosive agent of the present invention described in Table-1 (Examples 3, 4, and 11)
Table 2 shows the results obtained by adding to the rolling oil of the following components.

Processing oil A Mineral oil (Vis 40 ° C 9-12cst) 90% Emulsifier (nonionic activator) 5% Oiliness agent (higher alcohol) 5% Example 13 The rust preventive agent of the present invention described in Table-1 (Examples 3, 4, and 11)
Table 3 shows the results of adding the above-mentioned to the cutting oil of the following components.

Processing oil B Mineral oil (Vis 40 ° C 9-12cst) 55% Emulsifier (anion activator) 20% Oiliness agent (fatty acid ester) 15% Extreme pressure agent (chlorine type) 10% The test solution was a 1% aqueous solution for the wet pack test and a 0.5% aqueous solution for the immersion test.

〔The invention's effect〕

The rust preventive agent of the present invention has excellent water-stain resistance and oil-stain resistance of aluminum and aluminum alloys, such as rust and stains on plastic processed products such as plates, pipes and bars, and machined parts such as machines and automobiles. Generation is suppressed and good for a long time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C10M 133: 08 137: 04 137: 06 137: 08) C10N 10:02 30:12 40:24 A (56) References JP-A-60-202197 (JP, A) JP-A-51-69460 (JP, A) JP-A-54-94446 (JP, A) JP-A-50-92304 (JP, A) KO 44-10650 (JP, B1)

Claims (9)

[Claims] 1. A phosphoric acid partial ester (salt) of an oxyalkylated amine (a) or a hydroxyalkylamine (wherein the hydroxyalkyl group has 5 or more carbon atoms) represented by the general formula (1), which is an oxyalkylated product (b). A rust preventive agent for aluminum containing [A]. [Wherein R ₁ is an organic group having a hydrocarbon group of C ₄ or more; R ₂ is H, an organic group having a hydrocarbon group or A ₂ O) n ₂ H, or R ₁ and R ₂ are In some cases, CH ₂ m (m ′ is 4 to 4 are connected to each other via an oxygen atom or a nitrogen atom.
_{6), - CH 2 CH 2} OCH 2 CH 2 - or (R _'2 is H or an alkyl group C ₁ ~ ₄₎ may form a 5- to 7-membered ring together with next N. A ₁ and A ₂ are C _{2 to} C ₄ alkylene groups; n ₁ and n ₂ are integers of 1 or more. ] 2. The rust preventive agent according to claim 1, wherein R ₁ is a C ₄ or more alkyl or alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkaryl group. 3. (b) is a general formula (In the formula, R ₃ is a C ₃ or more aliphatic hydrocarbon group; R ₄ , R ₅ , and R ₆
Is H, an organic group having a hydrocarbon group or A ₃ O) n ₃ H, R ₇
Is H or A ₃ O) n ₃ H, and at least one of R ₄ , R ₅ , R ₆ , and R ₇ is A ₃ O) n ₃ H. A ₃ is an alkylene group of C ₂ -C _4, A is an alkylene group, m is 0 or an integer from 1 to 6,
n ₃ is an integer of 1 or more. R ₄ and R ₅ are optionally connected to each other via an oxygen atom or a nitrogen atom to form 5 together with N.
A ~ 7-membered ring may be formed. ] The rust preventive agent of Claim 1 or 2 shown by these. 4. A phosphoric acid partial ester (salt) of an oxyalkylated amine (a) or a hydroxyalkylamine (wherein the hydroxyalkyl group has 5 or more carbon atoms) represented by the general formula (1), which is an oxyalkylated compound (b). A rust preventive agent for aluminum comprising [A] and an alkanolamine [B]. [Wherein R ₁ is an organic group having a hydrocarbon group of C ₄ or more; R ₂ is H, an organic group having a hydrocarbon group or A ₂ O) n ₂ H, or R ₁ and R ₂ are In some cases, CH ₂ m (m ′ is 4 to 4 are connected to each other via an oxygen atom or a nitrogen atom).
_{6), - CH 2 CH 2} OCH 2 CH 2 - or (R _'2 is H or an alkyl group C ₁ ~ ₄₎ may form a 5- to 7-membered ring together with next N. A ₁ and A ₂ are C _{2 to} C ₄ alkylene groups; n ₁ and n ₂ are integers of 1 or more. ] 5. The weight ratio of [A] and [B] is 99.5: 0.5 to 50: 5.
The rust preventive agent according to claim 4, which is 0. 6. The rust preventive agent according to claim 4 or 5, wherein R ₁ is a C ₄ or more alkyl or alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkaryl group. 7. (b) is a general formula (In the formula, R ₃ is a C ₃ or more aliphatic hydrocarbon group; R ₄ , R ₅ , and R ₆
Is H, an organic group having a hydrocarbon group or A ₃ O) n ₃ H, R ₇
Is H or A ₃ O) n ₃ H, and at least one of R ₄ , R ₅ , R ₆ , and R ₇ is A ₃ O) n ₃ H. A ₃ is an alkylene group of C ₂ -C _4, A is an alkylene group, m is 0 or an integer from 1 to 6,
n ₃ is an integer of 1 or more. R ₄ and R ₅ are optionally connected to each other via an oxygen atom or a nitrogen atom to form 5 together with N.
A ~ 7-membered ring may be formed. ] The rust preventive agent of any one of Claims 4-6 shown by these. 8. [B] is a general formula [In the formula, R ₈ and R ₉ are H, a hydrocarbon group or A ₅ O) n ₅ H;
n ₄ and n ₅ are integers of 1 or more; A ₄ and A ₅ are C _{2 to} C ₄ alkylene groups. R ₈ and R ₉ may be linked to each other, optionally via an oxygen or nitrogen atom, to form a 5- to 7-membered ring with N. ] The rust preventive agent as described in any one of Claims 4-7 which is a compound shown by these. 9. The rust preventive agent according to claim 8, wherein the compound represented by the general formula (3) is a compound selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and cyclohexylaminoethanol.