JP2003082287A - Metal corrosion inhibitor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metal protective agent. SOLUTION: The metal protective agent having a various shape such as a wax, a lubricant or the like is prepared by mixing a mercaptoamidocarboxylic acid (salt) with a suitable base material. The metal protective agent expresses especially high potency for preventing corrosion of aluminum, so it is especially useful as the protective agent for aluminum.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the use of mercaptoamidecarboxylic acid as a metal protective agent.

[0002]

BACKGROUND OF THE INVENTION Metals are often used as structural and decorative materials in equipment and facilities such as vehicles and buildings. Preventing metal corrosion, maintaining metallic luster, and protecting metal are important for maintaining the aesthetics of equipment and facilities and preventing deterioration. For this purpose transparent paints and waxes are applied.

[0003]

In order to prevent metal corrosion, a large amount of paint or wax may be used or reapplied frequently to maintain a high corrosion prevention effect. The problem of these methods is that the method of using a large amount of paint or wax deteriorates the texture of the metal, and the method of frequently re-applying increases the amount of maintenance work, which is not preferable.

Not only that, but recently, from the viewpoint of environmental load, etc., it has been attempted to reduce wastes and positively reuse metal materials and parts. A metal protective agent that exhibits a high protective effect even when applied in a small amount is considered to be useful in that the effect of reducing wastes derived from the metal protective agent can be expected in the recycling process.

Development of a high-performance metal protective agent capable of preventing corrosion of a metal even if used in a small amount is an important issue.

[0006]

[Means for Solving the Problems] The problems described in the preceding section can be solved if a strong metal corrosion preventing effect can be imparted to metal protective agents such as paints and waxes. As a solution, it is possible to use a metal corrosion inhibitor as a component such as paint or wax to have a metal corrosion preventing effect.

The present inventor has studied how to use mercaptoamide carboxylic acid (salt), and found that a metal protective agent having various properties can be prepared by mixing with various bases, to complete the present invention. I arrived. The mercaptoamide carboxylic acid used herein means a compound having a mercapto group, an amide bond and a carboxyl group as constituents of the molecular structure, and details will be described later.

The present invention relates to the following items. [1] The following structural formula (1)

[0009]

[Chemical 2]

(Where C _n H _m and C _i H _j are hydrocarbon chains, n is an integer of 2 or more and 12 or less, m is an integer of 2 or more and 2n or less, i is 2 or more and 40 or less , J is 0 or more 2i + 1-k-z
The following integers, k is an integer of 1 or more and 5 or less, z is an integer of 1 or more and 5 or less, M is hydrogen or metal or ammonium
A metal protective agent obtained by dissolving and / or mixing a mercaptoamidecarboxylic acid (salt) represented by NH ₄ or ammonium derived from amine) in a base. [2] The metal protective agent according to [1], wherein an oily base which is liquid, paste, wax or solid is used as the base. [3] The metal protective agent or the lubricant having a metal protective action according to [1] or [2], wherein the base is a lubricant.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The substances of the present invention and the substances used in the present invention will be described.

The molecular structure of the mercaptoamidecarboxylic acid (salt) of the present invention is generally represented by the following structural formula (1).
Indicated by.

[0013]

[Chemical 3]

In the structural formula (1), C _n H _m and C _i H _j mean a hydrocarbon chain. n is an integer greater than or equal to 1, but usually
It is in the range of 2 to 12 inclusive. m corresponds to n, and is an integer of 2 or more and 2n or less. i is an integer of 2 or more, and is usually in the range of 2 or more and 40 or less. j corresponds to i, and is an integer of 0 or more and 2i + 1-k-z or less. k is
It is an integer of 1 or more, and usually in the range of 1 or more and 5 or less. z is an integer of 1 or more, and is usually in the range of 1 or more and 5 or less. M means a hydrogen atom, a metal atom, or ammoniums, that is, NH ₄ or ammonium derived from an amine. As a preferable condition for n and i, n is an integer of 2 or more and 12 or less, i is an integer of 8 or more and 40 or less, and a more preferable range of i is 12 or more and 30 or less.

This mercaptoamide carboxylic acid (salt) is composed of a mercaptoamine residue and a carboxylic acid residue in terms of molecular structure. In the present specification, the characteristics of the mercaptoamide carboxylic acid (salt) of the structural formula (1) will be described separately for the mercaptoamine residue and the carboxylic acid residue.

In the case of the mercaptoamine residue HS (C _n H _m ) NH, the minimum value of the number of carbon atoms n should be possible up to 1, but from the viewpoint of synthetic technology, the preferable minimum value of the number of carbon atoms n is 2. Become. The upper limit of the maximum value of the number of carbon atoms n is considered to be gradual, but practically it is considered to be about 12, preferably about 8. These upper limits are given as a guide in consideration of reasons such as synthesis, and it is possible to exceed the ranges shown here. The number m of hydrogen atoms corresponds to the number n of carbon atoms, and the minimum value is 2 and the maximum value is 2n. Summarizing the consideration of the range shown here, the number of carbon atoms n
The range of 1 can be 1 or more, but 2 or more and 12 or less is practical, and preferably 2 or more and 8 or less. Usually, those of 2 or more and 6 or less are particularly preferably used.

The hydrocarbon chain -C _n H _m - ethylene chain Specific examples of propylene chain, butene chain, pentene-chain, hexene chain such as - (CH _{2) y} - represented by (y = n) aliphatic hydrocarbons hydrogen chain, o- phenylene chain, m- phenylene chain, or a phenylene chain such as p- phenylene chain _{-C 6 H 3 (CH 3)} -, -C 6 H 4 CH
_{2 -, - CH 2 C 6} H 4 CH 2 - hydrocarbon chain having an aromatic ring such as may be exemplified. Of these, ethylene chains, propylene chains, phenylene chains and the like are preferable, and ethylene chains are particularly preferable. The structure of the hydrocarbon chain —C _n H _m — is considered to be equivalent to the structure of the hydrocarbon chain C _i H _j described later when k = 1 and z = 1. See also the description of the hydrocarbon chain C _i H _j . Specific examples of mercaptoamine residues are cysteamine residues, mercaptoaminopropane residues, mercaptoaminobutane residues, mercaptoaminopentane residues, mercaptoaminohexane residues, mercaptoaminocyclopentane residues,
Non-alicyclic or cycloaliphatic aliphatic mercaptoamine residues such as mercaptoaminocyclohexane residues and aromatic mercapto alcohol residues such as aminobenzenethiol residues are preferred choices. Among these, mercaptoethanol residues, mercaptoaminopropane residues, aminobenzenethiol residues and the like are more preferable examples of selection.

Carboxylic acid residue of structural formula (1) {--CO} _z
The number i of carbon atoms of C _i H _j (COOM) _k can be 0 or more, but 2 or more is advantageous in synthesis. When used as a hydrophobic metal protective agent such as wax Number of carbon atoms i
Is preferable, and for example, when it is applied to Mg, Al, Zn, etc., the one having a relatively large number of carbon atoms tends to be more effective. For this reason, the number of carbon atoms i is preferably 8 or more,
It is more preferably 12 or more. In particular, when the mercaptoamide carboxylic acid of structural formula (1) itself is used as a wax-like or solid-state metal protective agent, the more preferable carbon atom number i is 15 or more.

The upper limit of the number of carbon atoms i is considered to be gentle, but the upper limit considered to be practically easy to synthesize is about 40, the preferred upper limit is about 35, and the more preferred upper limit is about 30. The range of the number of carbon atoms i shown here can be summarized as 0 or more, but it is advantageous in terms of synthesis to be 2 or more, and usually 2 or more and 40 or less, but preferably It is 8 or more and 35 or less, and more preferably 12 or more and 30 or less. Particularly, the range of the number of carbon atoms i is preferably 15 or more and 30 or less in that the compound itself is in a wax form or a solid form.

The number j of hydrogen atoms corresponds to the number i of carbon atoms, and the minimum value is 0 and the maximum value is (2 i + 2-z−k).

Carboxylic acid residue of structural formula (1) {--CO} _z
In C _i H _j (COOM) _k , k can be described as an integer of 1 or more, and z can be described as an integer of 1 or more, but practical k is 5 or less, preferably k
Is 3 or less, a practical z is 5 or less, and a preferable z is 3 or less. As a concrete combination, k = 1, z = 1 or k
= 2, z = 1 or k = 3, z = 1 or k = 1, z = 2 or k = 2, z = 2 or k = 3, z = 2 or k = 1, z = 3 or k = 2 , Z = 3 or k = 3, z =
3 can be exemplified. More preferably, k = 1 and z = 1, and the corresponding mercaptoamidecarboxylic acid has a molecular structure of the following structural formula (2).

[0022]

[Chemical 4]

It is represented by

Specific examples of the hydrocarbon chain C _i H _j corresponding to k = 1 and z = 1 are methylene chain, ethylene chain, propylene chain, butene chain, pentene chain, hexene chain, heptene chain,
Octene chain, nonene chain, decene chain, undecene chain, dodecene chain, tridecene chain, tetradecene chain, pentadecene chain, hexadecene chain, heptadecene chain, octadecene chain, etc .- (CH ₂ ) _I- aliphatic hydrocarbon chain represented by _I- , Cyclobutene chain, cyclopentene chain, cyclohexene chain, cycloheptene chain, cyclooctene chain, cyclononene chain, cyclodecene chain, cycloundecene chain, cyclododecene chain, cyclotridecene chain, cyclotetradecene chain, cyclopentadecene chain, cyclohexadecene chain, cyclo heptadecene chain, cycloalkyl octadecene chain such as _{- (C i H 2i-2} ) -
In or cycloaliphatic hydrocarbon chain having a cyclic structure represented, phenylene chain -C ₆ H ₄ - or naphthylene chain -C ₁₀ H ₆ - and biphenylene chain -C ₆ H ₄ -C ₆ H ₄ - or -C ₆ H ₂ (CH ₃ ) ₂ −, −C ₆ H (CH
_{3) 3 -, - C 6} (CH 3) 4 -, -C 6 H 3 (C 2 H 5) -, - C 6 H 2 (C 2 H
₅ ) ₂₋ , −C ₆ H (C ₂ H ₅ ) ₃ −, −C ₆ (C ₂ H ₅ ) ₄ −, −C ₆ H _{3
(C 3 H 7) -,} - C 6 H 2 (C 3 H 7) 2 -, -C 6 H (C 3 H 7) 3 -, - C
₆ (C ₃ H ₇ ) ₄ −, −CH ₂ CH ₂ C ₆ H ₄ −, −CH ₂ C ₆ H ₄ CH ₂ −,
_{-CH 2 CH 2 C 6 H 4} -, - CH 2 CH 2 CH 2 C 6 H 4 -, -CH 2 CH 2 C 6 H 4 C
H ₂ -, phenyl naphthylene chain, a benzene ring as the aromatic hydrocarbon chain and its partial structure, such as binaphthylene chain, naphthalene ring, anthracene ring, hydrocarbon chain aromatic ring is present, such as phenanthrene may be exemplified .

As a partial structure of these hydrocarbon chains C _i H _j , for example, —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH (CH ₃ ) —, and further —CH ₂ CHR ^x — (R It is possible that a branched structure exists such that ^x is a hydrocarbon group). Further, an unsaturated bond such as a double bond may be present, and for example, a dihydrophenylene chain —C ₆ H ₆ —, a tetrahydrophenylene chain —C ₆ H ₈ —
And other -CH = CH-, -CH = CH- CH 2 -, - CH = C (CH 3)
_{-, -CH 2 C (= CH} 2) -, - CH 2 CH (CH 2 CH = CHC 9 H 19) -,
It can exist in various positions such as --CH ₂ CH (C ₁₂ H ₂₃ )-(C ₁₂ H ₂₃ is a dodecenyl group).

When k = 2 and z = 1, or when k = 1 and z = 2, the corresponding hydrocarbon chain C _i H _j is a hydrogen atom from the hydrocarbon chain corresponding to k = 1 and z = 1. It corresponds to the one that came off and became a bond. For example, a straight chain aliphatic saturated hydrocarbon chain C _i H _{j
The, -CH <, - C 2 H} 3 <, - C 3 H 5 <, - C 4 H 7 <,
-C ₅ H ₉ <, -C ₆ H ₁₁ <, -C ₇ H ₁₃ <, -C ₈ H ₁₅ <, -C ₉ H ₁₇
<, -C ₁₀ H ₁₉ <, -C ₁₁ H ₂₁ <, -C ₁₂ H ₂₃ <, -C ₁₃ H
₂₅ <, -C ₁₄ H ₂₇ <, -C ₁₅ H ₂₉ <, -C ₁₆ H ₃₁ <, -C ₁₇ H _{33
<, - C 18 H 35 <} , - C 19 H 37 < others. Examples of the aliphatic saturated hydrocarbon chain C _i H _j having a straight-chain aliphatic unsaturated hydrocarbon chain C _i H _j or cyclic _{structures, -C 2 H <, - C} 3 H 3 <, - C
_{4 H 5 <, - C 5} H 7 <, - C 6 H 9 <, - C 7 H 11 <, - C 8 H 13 <,
-C ₉ H ₁₅ <, -C ₁₀ H ₁₇ <, -C ₁₁ H ₁₉ <, -C ₁₂ H ₂₁ <, -C
₁₃ H ₂₃ <, -C ₁₄ H ₂₅ <, -C ₁₅ H ₂₇ <, -C ₁₆ H ₂₉ <, -C ₁₇
Examples include H ₃₁ <, −C ₁₈ H ₃₃ <, −C ₁₉ H ₃₅ <, and the like. As a hydrocarbon chain C _i H _j having an aromatic ring, -C ₆ H ₃ <, -C ₆ H
_{2 (CH 3) <, -} C 6 H (CH 3) 2 <, - C 6 H 2 (C 2 H 5) <-C 10 H 5 with those or naphthalene ring with a benzene ring such as <
It may be a hydrocarbon chain having an aromatic ring such as or anthracene ring or phenanthrene ring.

The hydrocarbon chain C _i H _j corresponding to k = 2 and z = 2 is equivalent to a hydrocarbon chain corresponding to k = 1 and z = 1 in which two hydrogen atoms have been removed to serve as a bond. To do. For example, as the straight-chain aliphatic saturated hydrocarbon chain C _i H _j ,> C <,> C ₂ H ₂ <,>
C ₃ H ₄ <,> C ₄ H ₆ <,> C ₅ H ₈ <,> C ₆ H ₁₀ <,> C ₇ H
₁₂ <,> C ₈ H ₁₄ <,> C ₉ H ₁₆ <,> C ₁₀ H ₁₈ <,> C ₁₁ H
₂₀ <,> C ₁₂ H ₂₂ <,> C ₁₃ H ₂₄ <,> C ₁₄ H ₂₆ <,> C ₁₅ H ₂₈
<,> C ₁₆ H ₃₀ <,> C ₁₇ H ₃₂ <,> C ₁₈ H ₃₄ <,> C ₁₉ H ₃₆ <
Can be exemplified. Examples of the aliphatic saturated hydrocarbon chain C _i H _j having a straight-chain aliphatic unsaturated hydrocarbon chain C _i H _j or cyclic _{structures,> C 2 <,> C} 3 H 2 <,> C 4 H 4 <, > C ₅ H ₆ <,> C ₆ H ₈
<,> C ₇ H ₁₀ <,> C ₈ H ₁₂ <,> C ₉ H ₁₄ <,> C ₁₀ H ₁₆ <,
> C ₁₁ H ₁₈ <,> C ₁₂ H ₂₀ <,> C ₁₃ H ₂₂ <,> C ₁₄ H ₂₄ <,>
C ₁₅ H ₂₆ <,> C ₁₆ H ₂₈ <,> C ₁₇ H ₃₀ <,> C ₁₈ H ₃₂ <,> C
₁₉ H ₃₄ <and the like can be exemplified. Hydrocarbon chain with aromatic ring C _i H
Examples of _j include> C ₆ H ₂ <,> C ₆ H (CH ₃ ) <,> C ₆ (C
H ₃ ) ₂ <,> C ₆ H (C ₂ H ₅ ) <,> C ₆ H (C ₃ H ₇ ) <,> C ₁₀ H ₄
Examples thereof include those having a benzene ring or a naphthalene ring, but may be a hydrocarbon chain having an aromatic ring such as an anthracene ring or a phenanthrene ring.

In these examples, "<" and ">" mean two bonds.

Examples of the carboxylic acid residue having a hydrocarbon chain C _i H _j described above include octenyl succinic acid residue, octanyl succinic acid residue, decenyl succinic acid residue, decanyl succinic acid residue, dodecenyl succinic acid residue, dodeca Nyl succinic acid residue, pentadecenyl succinic acid residue, pentadecanyl succinic acid residue, octadecenyl succinic acid residue, octadecanyl succinic acid residue, maleated methylcyclohexene tetrabasic acid residue, Methylnorbornene-2,3-dicarboxylic acid residue, methylendomethylenetetrahydrophthalic acid residue, succinic acid residue, maleic acid residue, methylsuccinic acid residue, citraconic acid residue, itaconic acid residue, glutaric acid residue , Tetrahydrophthalic acid residue, hexahydrophthalic acid residue, tetrahydromethylphthalic acid residue, cyclopentanetetracarbo Acid residue, endomethylenetetrahydrophthalic acid residue, hexahydromethylphthalic acid residue, and other aliphatic dicarboxylic acid residues, aliphatic polycarboxylic acid residues, and other chlorendic acid residues, such as chlorine atoms and fluorine With aliphatic dicarboxylic acid residue, phthalic acid residue, trimellitic acid residue, pyromellitic acid residue, mellitic acid residue, naphthalenedicarboxylic acid residue, biphenyldicarboxylic acid residue, phenylnaphthalenedicarboxylic acid residue ,
Aromatic dicarboxylic acid residues and aromatic polycarboxylic acid residues such as naphthylnaphthalenedicarboxylic acid residues and binaphthyldicarboxylic acid residues, and other phenylsuccinic acid residues,
Examples thereof include a carboxylic acid residue having an aromatic ring such as a phenylmaleic acid residue. Oxalic acid residues and malonic acid residues can also be used if there are no problems with the synthetic raw materials. Among these, octenyl succinic acid residue, octanyl succinic acid residue, decenyl succinic acid residue, decanyl succinic acid residue, dodecenyl succinic acid residue, dodecanyl succinic acid residue, pentadecenyl succinic acid residue, pentadecanyl Aliphatic dicarboxylic acid residues such as succinic acid residue, octadecenyl succinic acid residue, octadecanyl succinic acid residue and the like are preferable examples. Further, a phthalic acid residue, a trimellitic acid residue, a pyromellitic acid residue, a mellitic acid residue, a naphthalenedicarboxylic acid residue and the like are also preferable.

Therefore, structural formula (1) and structural formula (2)
As a preferred example of a mercaptoamide carboxylic acid represented by, a carboxylic acid residue having a mercaptoamine having a hydrocarbon chain C _n H _m and a hydrocarbon chain C _i H _j (dicarboxylic acid residue, Polycarboxylic acid residue).

Preferred examples of the mercaptoamide carboxylic acid which is a combination of a cysteamine residue and a carboxylic acid residue having a hydrocarbon chain C _i H _j include N- (mercaptoethyl) octenylsuccinamic acid and N- (Mercaptoethyl) octanylsuccinamic acid, N- (mercaptoethyl) decenylsuccinamic acid, N- (mercaptoethyl) decanylsuccinamic acid, N- (mercaptoethyl) dodecenylsuccinamic acid, N -(Mercaptoethyl) dodecanyl succinamic acid, N- (mercaptoethyl) pentadecenyl succinamic acid, N- (mercaptoethyl) pentadecanyl succinamic acid, N- (mercaptoethyl) octadecenyl succinamide Acid, N- (mercaptoethyl) octadecanyl succinamic acid and other N- (mercaptoethyl) N- (mercaptoethyl) aliphatic such as N- (mercaptoethyl) pentadecanedicarboxylic acid monoamide and N- (mercaptoethyl) hexadecanedicarboxylic acid monoamide such as alkenylsuccinamic acid and N- (mercaptoethyl) alkylsuccinamic acid Dicarboxylic acid monoamide, N- (mercaptoethyl) maleated methylcyclohexene tetrabasic acid monoamide, bis (N, N'-mercaptoethyl) maleated methylcyclohexene tetrabasic acid diamide, N- (mercaptoethyl) methylnorbornene-2,3 -Dicarboxylic acid monoamide,
N- (mercaptoethyl) methylendomethylenetetrahydrophthalic acid monoamide, N- (mercaptoethyl) succinamic acid, N- (mercaptoethyl) maleamic acid, N- (mercaptoethyl) methylsuccinamic acid,
N- (mercaptoethyl) citraconamidic acid, N- (mercaptoethyl) itaconamic acid, N- (mercaptoethyl) glutaric acid monoamide, N- (mercaptoethyl) tetrahydrophthalamic acid, N- (mercaptoethyl) hexahydrophthalic acid Amic acid, N- (mercaptoethyl) tetrahydromethylphthalamic acid, N- (mercaptoethyl) cyclopentanetetracarboxylic acid monoamide, bis (N, N'-mercaptoethyl) cyclopentanetetracarboxylic acid diamide, N- (mercaptoethyl) ) N- (mercaptoethyl) aliphatic dicarboxylic acid monoamides such as endomethylenetetrahydrophthalamic acid, N- (mercaptoethyl) hexahydromethylphthalamic acid and bis (N, N'-mercaptoethyl) aliphatic polycarboxylic diamides Have multiple N-mecaptoethyl Aliphatic Polycarbonate Polyamide Others Having chlorine atom or fluorine, such as N- (mercaptoethyl) chlorendic acid monoamide
N- (mercaptoethyl) aliphatic dicarboxylic acid monoamide, N- (mercaptoethyl) phthalamic acid, N- (mercaptoethyl) trimellitic acid, N- (mercaptoethyl) pyromellitic acid, N- (mercaptoethyl) mellitamide Acid, N- (mercaptoethyl) naphthalenedicarboxylic acid monoamide, N- (mercaptoethyl) biphenyldicarboxylic acid monoamide, N- (mercaptoethyl) phenylnaphthalenedicarboxylic acid monoamide, N-
N- (mercaptoethyl) such as (mercaptoethyl) naphthylnaphthalenedicarboxylic acid monoamide, N- (mercaptoethyl) binaphthyldicarboxylic acid monoamide, etc.
Aromatic dicarboxylic acid monoamides, bis (N, N'-mercaptoethyl) aromatic polycarboxylic acid diamides, aromatic polycarboxylic polyamides having a plurality of N-mecaptoethyl and others N- (mercaptoethyl) phenylsuccinamic acid, N- Examples thereof include N- (mercaptoethyl) carboxylic acid amide having an aromatic ring such as (mercaptoethyl) phenylmaleamic acid. N- (mercaptoethyl) oxalic acid monoamide and N- (mercaptoethyl) malonic acid monoamide can also be used if there are no problems with the synthetic raw material.

Among these, N- (mercaptoethyl)
Octenyl succinamic acid, N- (mercaptoethyl)
Octanyl succinamic acid, N- (mercaptoethyl)
Decenyl succinamic acid, N- (mercaptoethyl) decanyl succinamic acid, N- (mercaptoethyl) dodecenyl succinamic acid, N- (mercaptoethyl) dodecanyl succinamic acid, N- (mercaptoethyl) ) Pentadecenylsuccinamic acid, N- (mercaptoethyl)
N- (mercaptoethyl) alkenylsuccinamic acid such as pentadecanylsuccinamic acid, N- (mercaptoethyl) octadecenylsuccinamic acid, N- (mercaptoethyl) octadecanylsuccinamic acid and N- ( Mercaptoethyl) alkylsuccinamic acid and the like are more preferable examples. Further, N- (mercaptoethyl) trimellitic amide acid, N- (mercaptoethyl) pyromellitic amide acid, N- (mercaptoethyl) naphthalenedicarboxylic acid monoamide and the like are more preferable examples.

Mercaptopropanol residue and hydrocarbon chain
Preferred examples of the mercaptoamidocarboxylic acid having a combination of carboxylic acid residues having C _i H _j include N-
(Mercaptopropyl) octenyl succinamic acid,
N- (mercaptopropyl) octanylsuccinamic acid, N- (mercaptopropyl) decenylsuccinamic acid, N- (mercaptopropyl) decanylsuccinamic acid, N- (mercaptopropyl) dodecenylsuccinamic acid , N- (mercaptopropyl) dodecanylsuccinamic acid, N- (mercaptopropyl) pentadecenylsuccinamic acid, N- (mercaptopropyl) pentadecanylsuccinamic acid, N- (mercaptopropyl) octadecenyls Cucinamic acid, N- (mercaptopropyl)
N- (mercaptopropyl) alkenylsuccinamic acid such as octadecanylsuccinamic acid and N- (mercaptopropyl) pentadecanedicarboxylic acid monoamide such as N- (mercaptopropyl) alkylsuccinamic acid and N- (mercaptopropyl) N- (mercaptopropyl) aliphatic dicarboxylic acid monoamides such as hexadecanedicarboxylic acid monoamide, N- (mercaptopropyl) maleated methylcyclohexene tetrabasic acid monoamide, bis (N, N'-mercaptopropyl) maleated methylcyclohexene tetrabasic acid Diamide, N- (mercaptopropyl)
Methyl norbornene-2,3-dicarboxylic acid monoamide, N- (mercaptopropyl) methylendomethylene tetrahydrophthalic acid monoamide, N- (mercaptopropyl) succinamic acid, N- (mercaptopropyl) maleamic acid, N- (mercaptopropyl) Methylsuccinamic acid, N- (mercaptopropyl) citraconamic acid, N- (mercaptopropyl) itaconic acid, N-
(Mercaptopropyl) glutaric acid monoamide, N- (mercaptopropyl) tetrahydrophthalamic acid, N-
(Mercaptopropyl) hexahydrophthalamic acid,
N- (mercaptopropyl) tetrahydromethylphthalamic acid, N- (mercaptopropyl) cyclopentanetetracarboxylic acid monoamide, bis (N, N'-mercaptopropyl) cyclopentanetetracarboxylic acid diamide, N-
N- (mercaptopropyl) such as (mercaptopropyl) endomethylenetetrahydrophthalamic acid and N- (mercaptopropyl) hexahydromethylphthalamic acid
Like aliphatic dicarboxylic acid monoamides, bis (N, N'-mercaptopropyl) aliphatic polycarboxylic diamides, aliphatic polycarboxylic polyamides with multiple N-mecaptopropyl, and N- (mercaptopropyl) chlorendic acid monoamide. N- (mercaptopropyl) aliphatic dicarboxylic acid monoamide having chlorine atom or fluorine, N- (mercaptopropyl) phthalamic acid, N- (mercaptopropyl) trimellitic acid, N- (mercaptopropyl) pyromellitic acid, N- (mercaptopropyl)
Melitomic acid, N- (mercaptopropyl) naphthalenedicarboxylic acid monoamide, N- (mercaptopropyl) biphenyldicarboxylic acid monoamide, N- (mercaptopropyl) phenylnaphthalenedicarboxylic acid monoamide, N-
N- (mercaptopropyl) aromatic dicarboxylic acid monoamides such as (mercaptopropyl) naphthylnaphthalenedicarboxylic acid monoamide, N- (mercaptopropyl) binaphthyldicarboxylic acid monoamide and bis (N, N'-mercaptopropyl) aromatic polycarboxylic acid Acid diamide and N
-Aromatic polycarboxylic polyamides with multiple mecaptopropyl, etc. N- (mercaptopropyl) with aromatic rings such as N- (mercaptopropyl) phenylsuccinamic acid and N- (mercaptopropyl) phenylmaleamic acid Examples thereof include carboxylic acid amide. N- (mercaptopropyl) oxalic acid monoamide and N- (mercaptopropyl) malonic acid monoamide can also be used if there are no problems with the synthetic raw material.

Among these, N- (mercaptopropyl) octenylsuccinamic acid, N- (mercaptopropyl) octanylsuccinamic acid, N- (mercaptopropyl) decenylsuccinamic acid, N- (mercaptopropyl) Decanyl succinamic acid, N- (mercaptopropyl) dodecenyl succinamic acid, N- (mercaptopropyl) dodecanyl succinamic acid, N- (mercaptopropyl) pentadecenyl succinamic acid, N- (mercapto Propyl) pentadecanyl succinamic acid,
N- (mercaptopropyl) octadecenylsuccinamic acid, N- (mercaptopropyl) octadecanylsuccinamic acid and other N- (mercaptopropyl) alkenylsuccinamic acid and N- (mercaptopropyl) alkylsuccinamide Acids and the like are more preferable examples. Also,
N- (mercaptopropyl) trimellitic amide acid, N-
(Mercaptopropyl) pyromellitic amide acid, N-
(Mercaptopropyl) naphthalenedicarboxylic acid monoamide is also a more preferable example.

Aminobenzenethiol residue and hydrocarbon chain
Preferred examples of the mercaptoamidocarboxylic acid having a combination of carboxylic acid residues having C _i H _j include N-
(Mercaptophenyl) octenylsuccinamic acid,
N- (mercaptophenyl) octanylsuccinamic acid, N- (mercaptophenyl) decenylsuccinamic acid, N- (mercaptophenyl) decanylsuccinamic acid, N- (mercaptophenyl) dodecenylsuccinamic acid , N- (mercaptophenyl) dodecanylsuccinamic acid, N- (mercaptophenyl) pentadecenylsuccinamic acid, N- (mercaptophenyl) pentadecanylsuccinamic acid, N- (mercaptophenyl) octadecenyls Cucinamic acid, N- (mercaptophenyl)
N- (mercaptophenyl) alkenylsuccinamic acid such as octadecanylsuccinamic acid and N- (mercaptophenyl) pentadecanedicarboxylic acid monoamide such as N- (mercaptophenyl) alkylsuccinamic acid and N- (mercaptophenyl) N- (mercaptophenyl) aliphatic dicarboxylic acid monoamides such as hexadecanedicarboxylic acid monoamide, N- (mercaptophenyl) maleated methylcyclohexene tetrabasic acid monoamide, bis (N, N'-mercaptophenyl) maleated methylcyclohexene tetrabasic acid Diamide, N- (mercaptophenyl)
Methyl norbornene-2,3-dicarboxylic acid monoamide, N- (mercaptophenyl) methylendomethylene tetrahydrophthalic acid monoamide, N- (mercaptophenyl) succinamic acid, N- (mercaptophenyl) maleamic acid, N- (mercaptophenyl) Methylsuccinamic acid, N- (mercaptophenyl) citraconic acid, N- (mercaptophenyl) itaconamic acid, N-
(Mercaptophenyl) glutaric acid monoamide, N- (mercaptophenyl) tetrahydrophthalamic acid, N-
(Mercaptophenyl) hexahydrophthalamic acid,
N- (mercaptophenyl) tetrahydromethylphthalamic acid, N- (mercaptophenyl) cyclopentanetetracarboxylic acid monoamide, bis (N, N'-mercaptophenyl) cyclopentanetetracarboxylic acid diamide, N-
N- (mercaptophenyl) such as (mercaptophenyl) endomethylenetetrahydrophthalamic acid and N- (mercaptophenyl) hexahydromethylphthalamic acid
Like aliphatic dicarboxylic acid monoamides, bis (N, N'-mercaptophenyl) aliphatic polycarboxylic diamides, aliphatic polycarboxylic polyamides with multiple N-mecaptophenyls and other N- (mercaptophenyl) chlorendic acid monoamides. N- (mercaptophenyl) aliphatic dicarboxylic acid monoamide having chlorine atom or fluorine, N- (mercaptophenyl) phthalamic acid, N- (mercaptophenyl) trimellitic acid, N- (mercaptophenyl) pyromellitic acid, N- (mercaptophenyl)
Melitamic acid, N- (mercaptophenyl) naphthalenedicarboxylic acid monoamide, N- (mercaptophenyl) biphenyldicarboxylic acid monoamide, N- (mercaptophenyl) phenylnaphthalenedicarboxylic acid monoamide, N-
N- (mercaptophenyl) aromatic dicarboxylic acid monoamides such as (mercaptophenyl) naphthylnaphthalenedicarboxylic acid monoamide, N- (mercaptophenyl) binaphthyldicarboxylic acid monoamide and bis (N, N'-mercaptophenyl) aromatic polycarboxylic acid Acid diamide and N
-Aromatic polycarboxylic polyamides with multiple mechatophenyls, etc. N- (mercaptophenyl) with aromatic rings such as N- (mercaptophenyl) phenylsuccinamic acid and N- (mercaptophenyl) phenylmaleamic acid Examples thereof include carboxylic acid amide. N- (mercaptophenyl) oxalic acid monoamide and N- (mercaptophenyl) malonic acid monoamide can also be used if there are no problems with the synthetic raw material.

Among these, N- (mercaptophenyl) octenylsuccinamic acid, N- (mercaptophenyl) octanylsuccinamic acid, N- (mercaptophenyl) decenylsuccinamic acid, N- (mercaptophenyl) Decanyl succinamic acid, N- (mercaptophenyl) dodecenyl succinamic acid, N- (mercaptophenyl) dodecanyl succinamic acid, N- (mercaptophenyl) pentadecenyl succinamic acid, N- (mercapto Phenyl) pentadecanyl succinamic acid,
N- (mercaptophenyl) octadecenylsuccinamic acid, N- (mercaptophenyl) octadecanylsuccinamic acid and other N- (mercaptophenyl) alkenylsuccinamic acids and N- (mercaptophenyl) alkylsuccinamide Acids and the like are more preferable examples. Also,
N- (mercaptophenyl) trimellitic amide acid, N-
(Mercaptophenyl) pyromellitic amide acid, N-
(Mercaptophenyl) naphthalenedicarboxylic acid monoamide is also a more preferable example.

In the structural formulas (1) and (2), M is a hydrogen atom, a metal atom or ammonium
Means ammonium derived from NH ₄ and amines. Therefore, as a specific example of the mercaptoamide carboxylate, ammonium derived from polyethyleneimine, polyallylamine, or polyvinylamine is also included in the category of M. In the case of free mercaptoamide carboxylic acid, M becomes a hydrogen atom. When a metal atom is used as M, an alkali metal atom such as Li, Na, K, Rb, Cs or an alkaline earth metal atom such as Be, Mg, Ca, Sr, Ba or the like and Fe or C depending on the purpose.
Other metals such as lanthanoids such as o, Ni, Cu, Zn, Al, Sc, Y, La, Ce, Pr and Nd may be used. These mercaptoamide carboxylates can be prepared by neutralizing the free acid with a suitable base or base-analogous substance. Examples of bases and base-analogous substances include lithium oxide, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, sodium oxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium oxide, potassium hydroxide, potassium carbonate, hydrogen carbonate. Alkali metal oxides such as potassium, hydroxides, carbonates, hydrogen carbonates, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide,
Calcium hydroxide, calcium carbonate, strontium oxide, strontium hydroxide, strontium carbonate, barium oxide, barium hydroxide, barium carbonate such as alkaline earth metal oxides, hydroxides, carbonates, zinc oxide, zinc hydroxide, Zinc carbonate, copper oxide, copper hydroxide, copper carbonate and other metal oxides, hydroxides, carbonates, ammonia, ammonia water, ammonium carbonate, ammonium hydrogen carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, Monoamines such as triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, diaminobutane, diaminopentane, diaminohexane, diethylenetriamine, polyethyleneimine, polyallyl Min, such as diamines and polyamines such as polyvinylamine can be used. In addition, metathesis of the mercaptoamide carboxylate and the metal salt may be performed. In this case, preferably lithium salt, sodium salt, potassium salt, ammonium salt or the like can be used as the mercaptoamide carboxylate. The other metal salt is Fe, Co, Ni, Cu, Zn,
Various salts such as acetates, chlorides, sulfates and nitrates of lanthanoids such as Al, Sc, Y, La, Ce, Pr and Nd can be used.

The metal protecting agent of the present invention is a mercaptoamide carboxylic acid (salt) and a suitable oily base such as hydrocarbons such as paraffin, petrolatum, liquid paraffin and mineral oil, and higher fatty acid residues such as wax and higher alcohol residues. Esters formed from groups, animal fats and oils such as lard, beef tallow, whale fat, fish oil, castor oil, linseed oil, soybean oil, rapeseed oil, vegetable oils such as corn oil, resin such as pine resin, polyethylene, It is prepared by mixing polyolefin such as polypropylene. A paint may be used as a base, and a metal protective agent may be prepared as a rust / corrosion preventive paint. A lubricant may be used as a base. The lubricant here may be in the form of liquid, paste, wax or solid. When a paint or lubricant is used as the base, it may be not only oily but also water-based. This is because the water-based paint and the water-based lubricant have an oily component and thus can serve as an oily base for the mercaptoamide carboxylic acid (salt). In addition, water-soluble polymers such as polyvinyl alcohol, polyethylene glycol and polyethylene imine may be used as the base. Also in this case, a liquid, paste, wax or solid metal protective agent can be prepared. Recently, product design has been performed in consideration of the reuse of metals as materials and parts. It is considered preferable to easily remove the metal protective agent or the like adhering to the surface when the recovered metal or parts are reused or for temporary anticorrosion.
Most of the metal-protecting agents based on water-soluble polymers can be removed by washing with water if necessary. Therefore, using water-soluble polymers as a base is also a preferred choice.

The mixing ratio of the mercaptoamidecarboxylic acid (salt) and the base can be freely selected in principle, but it is usually 1: 9.
It is appropriate to select in the range 9 to 99: 1. However, it is not preferable that the mixing ratio of the mercaptoamide carboxylic acid (salt) becomes small because the protective effect of the metal decreases. It should be noted that when the mixing ratio of the mercaptoamide carboxylic acid (salt) becomes large, the physical properties of the metal corrosion inhibitor composition are almost determined by the physical properties of the mercaptoamide carboxylic acid (salt). Considering these points, the mixing ratio of mercaptoamide carboxylic acid (salt) and base is 5:95 to 8
It is preferable to determine in the range of about 0:20, and more preferable to determine in the range of 10:90 to 50:50. As a wax agent, setting the mixing ratio of mercaptoamide carboxylic acid and the base material to, for example, 10:85 to 30:70 makes it possible to change the physical properties of the composition by changing the base material while maintaining high protection performance. It is more preferable in that the range can be widened.

The metal protective agent of the present invention can be in the form of liquid, paste, wax, solid or the like at room temperature or under heating by selecting the mercaptoamide carboxylic acid (salt), the base and the mixing ratio thereof. The ones shown can be prepared.

Among the mercaptoamide carboxylic acids (salts), there are liquid, paste, wax and solid forms. These can be used as they are as a metal protective agent as they are, and the present invention does not prevent such usage.

The protective agent can be used, for example, by applying the protective agent in the form of liquid, paste, wax or solid onto cloth, paper or leather and performing the same treatment as usual waxing. Is. Alternatively, it can be used by directly coating it on the surface of the target metal requiring protection. Further, it may be dissolved in a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ligroin, kerosene, or light oil, or an ester such as ethyl acetate or butyl acetate to give a solution. The metal protective agent of the present invention liquefied by the method exemplified here or by heating can also be applied by a coating method such as brush coating, dipping, spraying or spin coating. It may also be used as a spray in a container such as a can. In this case, a container can be filled with a substance usually used as a propellant such as propane, butane, and dimethoxyethane, and the mixture can be sprayed in a mist state if necessary.

The metal protective agent of the present invention applied to the surface of an object by a method such as coating or spraying can exert the protective effect as it is, but at room temperature in air or an inert gas such as nitrogen or argon. Alternatively, it may be dried under heating to exert a protective effect.

Another method of using the metal protective agent of the present invention is to prevent corrosion of a metal existing in contact with a liquid such as water or an aqueous medium. Example 4 is an example of this. When the metal protective agent is put into water or an aqueous medium, it comes into contact with and adheres to the metal surface to be protected due to factors such as motion due to liquid flow and surface tension. At this time, the mercaptoamide carboxylic acid contained in the metal protective agent is adsorbed or adhered to the metal surface to exert an anticorrosion effect. The metal protective agent used here can have various shapes such as a plate shape, a rod shape, a small lump shape, and a fine particle shape according to the purpose.

The metal protective agent of the present invention is dissolved in a hydrocarbon such as hexane, heptane, benzene, toluene and xylene, a hydrocarbon mixture such as gasoline, kerosene, light oil and heavy oil, and an organic solvent such as ether, ethyl acetate and acetone. be able to. Therefore, it is also possible to protect the metal with which the oil agent, the fuel oil, the lubricant (lubricating oil) or the like contacts by mixing with the oil agent, the fuel oil, the lubricant (lubricating oil) or the like.

The metal protective agent of the present invention is an iron-based metal such as iron or an iron alloy such as iron, carbon steel or stainless steel, a copper alloy such as copper, brass or white copper, zinc or a zinc alloy, magnesium or a magnesium alloy, aluminum. And aluminum alloys, nickel and nickel alloys, chrome and chrome alloys, lanthanoids such as neodymium and their alloys, and lead, tin, manganese, cobalt, molybdenum, tungsten, vanadium, cadmium and their alloys. Among the metals exemplified here, iron and iron alloys, copper and copper alloys, zinc and zinc alloys, aluminum and aluminum alloys, magnesium and magnesium alloys, etc. are very widely used, but the metal of the present invention Protective agents are preferred as these anticorrosive agents. The metal protective agent of the present invention is particularly useful as an aluminum protective agent, a magnesium protective agent, a zinc protective agent, etc., because it exhibits a remarkable effect on the corrosion protection of a metal having a high ionization tendency.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The mercaptoamide carboxylic acid used particularly preferably was abbreviated as CODS, but its chemical structure is as follows. CODS: HSCH ₂ CH ₂ NHCOC ₂ H ₃ (C ₁₈ H ₃₅ ) COOH (COC ₂ H ₃ (C ₁₈ H ₃₅ ) COOH: Octadecenylsuccinic acid residue) [Example 1] (1) CODS 0.5 g Paraffin (9.5 g) was added to the mixture and heated to 70 ° C. to melt it. The resulting homogeneous solution was cooled to room temperature and waxy solid (5% CODS-paraffin) 1
I got 0 g. (2) 9.0 g of paraffin was added to 1.0 g of CODS and heated to 70 ° C. to melt it. The resulting homogeneous solution was cooled to room temperature to obtain 10 g of waxy solid (10% CODS-paraffin). (3) Paraffin 8.0 in CODS 2.0 g
g was added and heated to 70 ° C. to melt. The resulting homogeneous solution was cooled to room temperature to obtain 10 g of waxy solid (20% CODS-paraffin). (4) Paraffin in 4.0 g of CODS
6.0 g was added and heated to 70 ° C. to melt. The resulting homogeneous solution was cooled to room temperature to obtain 10 g of waxy solid (40% CODS-paraffin).

Example 2 A wax-like solid matter prepared in Example 2 in a square of 70 mm on a clean cold-rolled steel sheet surface was prepared.
A solution of g in 4.5 ml of cyclohexane 49
Microliter was applied and dried at room temperature. Under these conditions, the coating density of the waxy solid is 0.1 mg / cm ²
And its thickness was estimated to be about 1 μm. C
In the case of ODS and paraffin, the same operation was performed to apply the cold-rolled steel sheet surface. A cross-shaped linear scratch was made on the coating film using a knife, and salt water was sprayed to examine the corrosion prevention performance. After spraying with salt water for 2.5 hours, the state of corrosion was observed. As a control, the one to which paraffin was applied showed the onset of corrosion (the relative area of the discoloration area to the total area was about 90%), and in particular a continuous discoloration area of about 2 mm width was formed along the crosshairs. It was In the case where 10% CODS-paraffin was applied, the area of the corrosion initiation portion was small, and the corrosion portion along the crosshairs was also discontinuous, and corrosion was suppressed. The relative area of the color change area other than the crosshairs was about 10%. Those coated with 20% CODS-paraffin were also tested. Corrosion was suppressed as a whole as compared with the case where 10% CODS-paraffin was applied, and the relative area of the discolored area other than the portion along the crosshairs was about 2% or less. When CODS was applied, almost no corrosion was observed and no discolored area along the crosshairs was observed.

[Example 3] A solution prepared by dissolving 0.5 g of the wax-like solid prepared in Example 2 in 4.5 ml of cyclohexane was applied to each side of both sides of a tape-shaped aluminum foil piece having a width of 20 mm and a length of 50 mm. 10 microliters was applied and dried at room temperature. Under these conditions, the coating density of the waxy solid is 0.1 mg / cm ² and its thickness is
It was estimated to be about 1 μm. In the case of CODS or paraffin, the same operation was performed to apply it on the surface of the aluminum foil piece. This test piece was immersed in a 3% aqueous sodium chloride solution containing acetic acid (concentration: 5 mmole / liter) and sodium acetate (5 mmole / liter) for 5 days.

As a control, whitening and pitting corrosion were observed on the whole when paraffin was applied. In the case of coating with 10% CODS-paraffin, whitening and pitting corrosion were observed only in the coating defect portion, but the extent of corrosion was suppressed compared to the control. 20% COD
No corrosion was observed when S-paraffin was applied or when CODS was applied, except that the defective portion of the coating was slightly discolored.

[Embodiment 4] This embodiment was carried out considering not only a simple coating agent but also the possibility of being used as a water-dispersible corrosion inhibitor (corrosion preventing wax).

Since the basic composition of the test solution was a 3% aqueous sodium chloride solution containing acetic acid (concentration 5 mmole / liter) and sodium acetate (5 mmole / liter), the pH of the test solution was set to be about the same as pKa (4.8) of acetic acid. It was good. This was called the basic test solution, and the sample was dispersed.

When paraffin or the CODS-paraffin mixture prepared in Example 2 was used as a sample, 0.1 g of the sample was added to 30 ml of the basic test solution, heated to 80 ° C. and vigorously mixed to disperse the sample, followed by rapid cooling. And used as a test solution. CODS
In the case of only, it was 0.02% (200 ppm), but was added as a 5% isopropyl alcohol solution. 5 for these test solutions
The aluminum foil test piece was dipped for a day to examine the corrosion prevention effect. When CODS was used or when 40% CODS-paraffin was used, neither corrosion nor discoloration of the test piece was observed. 20% CODS
-When paraffin was used, white rust was observed on the test piece.When 10% CODS-paraffin or 5% CODS-paraffin was used, white rust was generated and pitting corrosion near the liquid surface was observed. Although seen, the degree of corrosion was high when 5% CODS-paraffin was used. When paraffin was used as a control, the degree of corrosion was severe, and white rust and pitting were generated on the whole, and most of the test pieces were cut near the liquid surface. [Synthesis Example 1] Synthesis of N-mercaptoethyl octadecenylsuccinamic acid (CODS). In a 300 ml eggplant-shaped flask, 35.0 g (0.1
mole) and DMT 11.7 g (0.1 mole) and heat to 70 ℃ to melt octadecenyl succinic anhydride while DMT
Mixed with. After reacting for 3 hours, 9 ml of water (0.5 mo
le) was added and heated to 100 ° C. for 3 hours. At this time, distillation of acetone was observed. Water was removed by placing under reduced pressure to obtain 42.7 g of CODS as a waxy solid.

[0054]

The mercaptoamide carboxylic acid (salt) is
The composition mixed with a suitable base material is useful as a metal protective agent. The metal protective agent may have various shapes such as wax and lubricant. The metal protective agent of the present invention is particularly useful as an aluminum protective agent because it exhibits particularly high performance in preventing corrosion of aluminum.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23F 11/00 C23F 11/00 G 11/12 101 11/12 101 11/14 101 11/14 101 11 / 16 11/16 // C10N 30:12 C10N 30:12

Claims (3)

[Claims] 1. The following structural formula (1): (However, in the formula, C _n H _m and C _i H _j mean a hydrocarbon chain, and n
Is an integer of 2 or more and 12 or less, m is an integer of 2 or more and 2n or less, i is an integer of 2 or more and 40 or less, j is an integer of 0 or more and 2i + 1-k-z or less, k
Is an integer of 1 or more and 5 or less, z is an integer of 1 or more and 5 or less, M is hydrogen or a metal or ammonium, that is, NH ₄ or ammonium derived from amine), and a mercaptoamide carboxylic acid (salt) as a base A metal protective agent dissolved and / or mixed in. 2. The metal protective agent according to claim 1, wherein an oily base which is liquid, paste, wax or solid is used as the base. 3. The metal protective agent or the lubricant having a metal protective action according to claim 1, wherein the base is a lubricant.