JPH05255873A - Corrosion inhibiting composition - Google Patents

Abstract

PURPOSE: To develop a corrosion inhibitor for ferrous metals in contact with water systems by compounding a specific ratio of aminobenzoic acid or its water-soluble salt and, if necessary, alkali metal borate with a carboxylic acid corrosion inhibitor, such as triazine-carboxylic acid or its water-soluble salt.

CONSTITUTION: The aminobenzoic acid expressed by formula IV or its water-soluble salt is mixed at 10 to 60 wt.% and further, the alkali metal borate expressed by formula IV at 10 to 6 wt.% at need with 40 to 90 wt.% carboxylic acid corrosion inhibitor consisting of one kind among the triazine-carboxylic acid expressed by formula I, such as 2,4,6-tris(5-carboxybentylamino)-1,3,5- triazine, and its water-soluble salt, the sulfonamidocarboxylic acid expressed by formula II or its water-soluble salt and the dicarboxylic acid expressed by formula III or its water-soluble salt. The corrosion inhibitor compsn. excellent to the ferrous metals even when used for the hard water systems is obtd.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to compositions for inhibiting corrosion.

[0002]

BACKGROUND OF THE INVENTION A wide variety of different chemical structures have found use as corrosion inhibitors for metals that come into contact with corrosive media in use.

One such group of compounds is the carboxylic acid compound. An example of a group of carboxylic acid compounds which are highly effective corrosion inhibitors for ferrous metals in contact with aqueous systems is described in US Pat. No. 4,402,907 and has the formula: {In the formula, Z is, for example, an alkylene group having 1 to 11 carbon atoms, R ₁ and R ₂ independently represent, for example, a hydrogen atom or a methyl group; and R ₃ is, for example, a group: —NR ₄ R
₅ [in the group, R ₄ represents an alkyl group having 1 to 12 carbon atoms or -Z-COOH (Z represents the above-mentioned meaning), and R ₅ represents a hydrogen atom or an alkyl group having 12 carbon atoms. .. ]] Is represented. } It consists of the compound represented by these, or its water-soluble salt.

Known, for example, as corrosion inhibitors for aqueous iron metals are also o-aminobenzoic acid (anthranilic acid) and its derivatives; see, for example, Kriss et al Zh. Prikl. Chem, 1
989, 62 (8), 1844-9.

[0005]

These known carboxylic acid corrosion inhibitors are disadvantageous when they are used in a hard water system because they tend to be less effective.

European Patent 341536 describes an attempt to improve protection from corrosion and the hard water sensitivity of anthranilic acid derivatives by combining them with alkenylsuccinic acid and alkanolamines.

[0007]

By constructing different carboxylic acid corrosion inhibitor formulations, we now find that the resulting formulations have outstanding corrosion inhibition properties with very low sensitivity to the environment of hard water. It was

Accordingly, the present invention is a corrosion inhibitor composition, based on its total weight: A) A1) a triazino-carboxylic acid of formula I as defined above; A2) II: (In the formula, R ₆ and R ₇ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m is an integer in the range of 1 to 10.) Acid; and A3) a dicarboxylic acid represented by formula III: HOOC- (CH ₂ ) _n- COOH III (wherein n represents an integer in the range of 4 to 12) or a mixture thereof; 40 to 90% by weight of a carboxylic acid corrosion inhibitor, or a water-soluble salt thereof; B) Formula IV: (In the formula, R ₈ is a hydrogen atom or the following formula V or VI Represents a group represented by. ) 1 of aminobenzoic acid represented by
10 or 60% by weight of one or more or one or more of its water-soluble salts; optionally C) Formula VII: NR ₉ R ₁₀ R ₁₁ VII, wherein R ₉ , R ₁₀ and R ₁₁ Independently, a hydrogen atom,
Optionally represents a straight-chain or branched C 1 -C 12 alkyl group interrupted by an oxygen atom, or R ₉ , R ₁₀ and R ₁₁ are of the formula VIII: (In the formula, R ₁₂ and R ₁₃ independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and p and q are independently 0 or in the range of 1 to 10. Where p and q are not 0 at the same time, and at least one of R ₉ , R ₁₀ and R ₁₁ represents a group of formula VIII). %, And optionally D) 0 to 10% by weight alkali metal borate; a corrosion inhibitor composition.

Z which is an alkylene group having 1 to 11 carbon atoms is, for example, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n
A decylene group and an n-undecylene group. Preferred such groups are alkylene groups having 1 to 5 carbon atoms, especially the n-pentylene group.

R ₆ and / or R ₇ which are alkyl groups having 1 to 4 carbon atoms are, for example, methyl group, ethyl group,
It is an n-propyl group, an isopropyl group or an n-butyl group. Preferably, R ₆ and R ₇ are independently a hydrogen atom or a methyl group, and a particularly preferred embodiment is when R ₆ is a methyl group and R ₇ is a hydrogen atom.

R ₄ , R ₅ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ which are alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group and isopropyl group. , N-butyl group, n-hexyl group, n-octyl group, n-decyl group or n-dodecyl group.

R ₉ , R ₁₀ and R ₁₁ which are alkyl groups having 1 to 12 carbon atoms interrupted by an oxygen atom are:
For example, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 1- or 2-methoxybutyl group, 1-methoxyoctyl group, 1-methoxydecyl group or 1 A methoxydodecyl group.

In formula III, n is preferably 11 and / or 12.

Preferably, R ₄ has 1 to 8 carbon atoms.
Or an alkyl group of -Z-COOH (Z represents an alkylene group having 1 to 5 carbon atoms), R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₉ and R ₁₀ Independently hydrogen atom and carbon atom 1
Or an alkyl group of formula VIII (wherein R ₁₂ and R ₁₃ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and at the same time, R ₁₁ is of formula VIII (wherein R ₁₂ and R ₁₃ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Accordingly, preferred compounds A1) are those in which R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, and R ₃
Is a group: —NR ₄ R ₅ (wherein R ₄ represents an alkyl group having 1 to 8 carbon atoms or —Z—COOH, and R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, And Z represents an alkylene group having 1 to 5 carbon atoms), or a water-soluble salt thereof; preferred compound A2) in which R ₆ and R ₇ are independently a hydrogen atom or a methyl group. A compound of formula II, or a water-soluble salt thereof; and a preferred compound A3)
Is an acid of formula III in which n is 11 or 12, an acid of formula III in which n is 11 and a formula III in which n is 12
And a water-soluble salt of the acid and the mixture of the acids.

Examples of specific compounds of formula I are: 2,4,6-tris (5'-carboxypentylamino) -1,3,5-triazine, 2,4,6-tris. (Carboxymethylamino) -1,3,5-triazine 2,4,6-tris (3′-carboxypropylamino) -1,3,5-triazine, 2,4,6-tris (4′-carboxybutyl) Amino) -1,3,5-triazine, 2,4,6-tris (11'-carboxyundecylamino) -1,3,5-triazine, 2,4,6
-Tris (5'-carboxypentyl-N-methylamino) -1,3,5-triazine, 2,4,6-tris (carboxymethyl-N-methylamino) -1,3,5
-Triazine, 2,4,6-tris (3'-carboxypropyl-N-methylamino) -1,3,5-triazine, 2,4-bis (5'-carboxypentylamino)
-6-n-octylamino-1,3,5-triazine,
2,4-bis (2'-carboxyethylamino) -6-
n-octylamino-1,3,5-triazine, 2,4
-Bis (2'-carboxyethylamino) -6-diethylamino-1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6-butylamino-1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6-ethylamino-1,3,5
-Triazine, 2,4-bis (3'-carboxypropylamino) -6-ethylamino-1,3,5-triazine, 2,4-bis (3'-carboxypropylamino)
-6-n-octylamino-1,3,5-triazine,
2,4-bis (3'-carboxypropylamino) -6
-N-propylamino-1,3,5-triazine, 2,
4-bis (carboxymethylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis (carboxymethylamino) -6-dodecylamino-1,
3,5-triazine, 2,4-bis (3'-carboxypropyl-N-methylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis (carboxymethyl-N- Methylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis (carboxyethyl-N-methylamino) -6-n-octylamino-1,3,5-triazine, 2 , 4-bis (5'-
Carboxypentylamino) -6- (2 ″ -carboxyethylamino) -1,3,5-triazine, 2,4-bis (5′-carboxypentylamino) -6- (carboxymethylamino) -1,3 , 5-triazine, 2,4
-Bis (3'-carboxypropylamino) -6-
(2 ''-carboxyethylamino) -1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6- (5 ''-carboxypentylamino-1,
3,5-triazine, 2,4-bis (3′-carboxypentylamino) -6- (5 ″ -carboxypentylamino-1,3,5-triazine.

The compounds of formula I are not new. These compounds and their preparation are described, for example, in Zhuranl.
Analiticheskoi Khimi 1
5 , 419-423 (1960), German Patent DE-OS
1993010, German Patent DE-OS 2819796
U.S. Pat. No. 3,697,520 and J. Pr
akt Chemie 23 173-85 (196
3). Particularly preferred compounds are 2,4
6-tris (5-carboxypentylamino) -1,
3,5-triazine and its water-soluble salts.

Examples of compounds of formula II are benzenesulfonamidoacetic acid, benzenesulfonamido-2-propionic acid, benzenesulfonamido-4-butyric acid, benzenesulfonamido-6-n-hexanoic acid, benzenesulfonamido- 8-n-octanoic acid, benzenesulfonamido-10-n-decanoic acid, N-methylbenzenesulfonamidoacetic acid, 4-toluenesulfonamidoacetic acid and N
-Methyl-4-toluenesulfonamidoacetic acid. Particularly preferred compounds are p-toluenesulfonamidocaproic acid and its water-soluble salts.

The compound represented by the formula III is, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-1,9-dioic acid, decane-1,10-dioic acid, undecane-1, 11-diacid and dodecane-1,
12-Diacids and their mixtures, such as the commercial mixture of undecane-1,11-dioic acid and dodecane-1,12-diacid sold as "Allox 232" and are mentioned last. Those are especially preferred.

Specific examples of aminobenzoic acid of formula IV are anthranilic acid and N- (2-carboxybenzyl) -2-aminobenzoic acid.

Optional alkanolamines of formula VII include, for example, ethanolamine, diethanolamine,
Triethanolamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, butylethanolamine, dibutylethanolamine, di-isopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanolamine, di-isopropanolamine, tri-isopropanolamine, no. It can be dibutanolamine, di-secondary butanolamine, tri-secondary butanolamine, or dimethylisopropanolamine. A particularly preferred alkanolamine is triethanolamine.

The alkali metal borate may be, for example, sodium borate or potassium borate.

Water-soluble salts of carboxylic acid compounds of the formulas I and / or II are alkali metal salts such as sodium or potassium salts; alkaline earth metal salts such as calcium or magnesium salts; or methyleneamine, ethyleneamine, isopropylamine. , Alkylamine salts having 1 to 12 carbon atoms, such as dibutylamine, tributylamine, octylamine or dodecylamine salts. The amine salts having 1 to 12 carbon atoms may be hydroxy-substituted as well as mono-,
It may be a di- or tri-ethanolamine salt.

As already indicated, the corrosion-inhibiting composition according to the invention provides an excellent inhibitory effect on the corrosion of ferrous metals in contact with aqueous media.

Accordingly, the present invention also provides a corrosion-inhibiting composition as defined above in an aqueous system in an effective amount for inhibiting corrosion, preferably 0.001 to 5% by weight based on the weight of the aqueous system.
To provide a method of suppressing corrosion of ferrous metal in contact with an aqueous system, the method comprising:

The aqueous system treated by the method of the present invention may be a total aqueous medium or a partial aqueous medium.

Water systems that can effectively carry out the treatment according to the present invention include, for example, cooling water systems, steam generation systems, seawater evaporators, reverse osmosis devices, bottle washing devices, papermaking devices, sugar evaporation devices, soil irrigation systems, and water pressure cooking devices. , Gas cleaning system, closed circulation heating water system,
Water based refrigeration systems, deep well water systems, aqueous machining fluid formations (eg, drilling, milling, reamer threading, broaching, drawing, turning,
In cutting, sawing, grinding and threading operations, or in non-cutting, spinning (spinnin
g), for use in drawing or rolling operations],
Includes aqueous refining systems, aqueous glycol antifreeze systems, water / glycol hydraulic liquids, and water-based polymeric surface coating systems.

The corrosion inhibiting composition of the present invention can be used in the method of the present invention alone or in combination with other materials known to be effective in water treatment.

In the treatment of completely aqueous systems, such as cooling water systems, steam generation systems, seawater evaporator systems, water pressure cookers and closed circulation heating systems, for example, one or more other water treatment additives may be used. Corrosion inhibitors; metal deactivators; other scale inhibitors / dispersants; threshold agents
s); precipitant; oxygen scavenger; sequestering agent; antifoam and biocide.

Other corrosion inhibitors which may be used are water-soluble zinc salts; phosphates; polyphosphates; phosphonic acids or their salts such as hydroxyethyldiphosphonic acid (HEDP), nitrilotrimethylenephosphonic acid, methylamino. Dimethylenephosphonocarboxylic acids and their salts (for example DE-OS 2632774).
Those substances shown in No. ), Hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and their substances shown in British Patent GB-PS1572406; nitrates such as sodium nitrate; nitrites such as sodium nitrite. Tungstates and molybdates such as tungstic acid or sodium molybdate; silicic acids such as sodium silicate; N-acyl sarcosines; N-acyl iminodiacetic acids; ethanolamines; aliphatic amines; and polycarboxylic acids. Maleic anhydride copolymers with acids, such as polymaleic acid and polyacrylic acid (and their respective alkali metal salts), such as sulfonated styrene, such as copolymers of acrylic acid with hydroxyalkylated acrylic acid and polymeris Containing acid and substituted derivatives of polyacrylic acid and copolymers thereof.

For metal deactivators, especially for copper, benzotriazole, 5,5'methylenebis-benzotriazole or copper-inactivated benzotriazole or toltriazole derivatives, or Mannich base derivatives thereof, or Includes mercaptobenzotriazole.

Scale inhibitors / dispersants include polymerized acrylic acid (or salts thereof), phosphino-polycarboxylic acids (for example those substances described in British Patent PS 1458235), European Patent PS015080.
No. 6, cotelomers, hydrolyzed polyacrylonitrile, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide and acrylic and methacrylic acid, lignin sulfonic acid and its salts, tannin naphthalene sulfonic acid / Formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (eg US Pat.
S-4029577), styrene / maleic anhydride copolymers and sulfonated styrene homopolymers (eg US Pat.
No. 4374733, those substances and combinations thereof).

The limiting agent to be mentioned is 2-phosphonobutane-
1,2,4-tri-carboxylic acid, HEDP, hydrolyzed polymaleic anhydride and salts thereof, alkylphosphonic acids, hydroxyphosphonoacetic acid, 1-amino-alkyl-1,1-diphosphonic acids and salts thereof, And alkali metal polyphosphates.

It will be apparent from the above list that certain additive compounds, such as phosphonocarboxylic acids, act as both scale inhibitors as well as corrosion inhibitors.

Precipitating aids which can be used are alkali metal orthophosphates or carbonates; oxygen scavengers contain alkali metal sulfites and hydrazines; sequestrants are nitrilotriacetic acid and its salts; Antifoaming agents include ethylene oxide and / or propylene oxide condensates and their ethylene oxide condensates added to silicones such as polydimethylsiloxane, distearyl sebacimide, distearyl adipamide and aliphatic alcohols such as capryl alcohol. It relates to derived products. Biocides which can be used are, for example, amines, quaternary ammonium compounds, m-chlorophenols, sulfur-containing compounds such as sulfones, methylenebisthiocyanates and carbamates, isothiazolines, brominated propionamides, Organazine compounds such as triazines, phosphonium compounds, chlorine and chlorine releasing agents, bromine and bromine releasing agents and tributyltin oxide.

If the system treated according to the invention is not a completely aqueous system such as an aqueous machined liquid formulation, it may be, for example, a water-dilutable cutting or grinding fluid.

The aqueous machined liquid formulation of the present invention may be, for example, a metalworking formulation. "Metalworking" means "reaming, broaching, stretching, spinning"
, Cutting, crushing, drilling, grinding, turning, sawing (sawin
g), "non-cutting or rolling". Examples of water-dilutable cutting or grinding solutions to which a corrosion-inhibiting compound of the formula I may be added include: a) at a dilution of 1:50 to 1: 100 used,
Aqueous stock solutions of one or more corrosion inhibitors, and optionally one or more antiwear agents, which are usually used as grinding solutions; b) biocides, corrosion inhibitors and antiwear agents. Polyglycol containing agent, which is 1:20 to 1: 4 for cutting operations
Used at 0 dilution, 1:60 to 1:80 for grinding
C) a semi-synthetic cutting solution similar to b) but additionally containing a surfactant for rendering the water-diluted product translucent and 10 to 25% oil; d) eg an emulsifier. , An emulsifying mineral oil stock solution containing a corrosion inhibitor, an extreme pressure / antiwear agent, a biocide, an antifoaming agent, a coupling agent, etc .; usually milky milk diluted to 1:10 to 1:50 Emulsifiers; e) Products similar to d) but containing less oil and more emulsifiers, which are diluted in the range 1:50 to 1: 100 and used for cutting or grinding operations. It becomes a transparent emulsion.

Mixtures of sodium nitrite and triethanolamine have been used as corrosion inhibitors in metalworking, but because of toxicity problems, for example due to the risk of N-nitrosamine formation, and in some countries. Alternatives to the use of sodium nitrite have been sought due to legal regulations on wastewater.

For partially aqueous systems where the aqueous component is an aqueous machined liquid formulation, the corrosion inhibitor composition of the present invention may be used alone or, for example, other known corrosion inhibitors and / or polar agents. It can be used as a mixture with other additives such as pressure additives.

Examples of other corrosion inhibitors which may be used in these aqueous systems in addition to the corrosion inhibitor composition of the present invention include the following groups: a) other organic acids, their esters or ammonium. , Amines, alkanolamines and metal salts,
They are, for example, benzoic acid, p-tert-butylbenzoic acid, triethanolamine laurate, iso-nonanoic acid, N-
Sodium lauroyl sarcosinate or nonylphenoxyacetic acid; b) Nitrogen-containing substances of the following types: alkanolamide fatty acids; imidazolines such as 1-hydroxyethyl-2-oleyl-imidazoline; oxazolines; triazoles such as benzotriazole. , Triethanolamine; fatty amines; inorganic salts such as sodium nitrate; c) phosphorus-containing substances of the following types: amine phosphates, phosphonic acids or inorganic salts such as sodium dihydrogen phosphate or zinc phosphate; d ) Sulfur-containing compounds such as: sodium petroleum sulfonate, calcium or barium, or heterocyclic compounds such as sodium mercaptobenzothiazoles.

Nitrogen-containing materials, especially triethanolamine, are preferred.

Examples of extreme pressure additives that may be present in the system of the present invention are those containing sulfur and / or phosphorus and / or halogen atoms, for example sulfurized sperm whale oil, sulfurized oils and fats,
It contains tritriyl phosphate, chlorinated paraffin or ethoxylated phosphate.

When triethanolamine is present in the water system treated according to the invention, the ratio of the corrosion inhibitor composition of the invention to triethanolamine is from 2: 1 to 1: 2.
It is preferably present in an amount such as zero.

The partially aqueous water system treated by the method of the present invention may be a surface-coating composition such as a primer emulsion paint for metallic substrates and an aqueous powder paint.

Aqueous surface-coating compositions include, for example, styrene-acrylic copolymer emulsion paints, resins,
It may be a paint such as a latex or other water based polymer surface-coating system.

Sodium nitrite and sodium benzoate have been used to control flash rust in water-based primer coatings, but with associated toxicity issues and emulsions at the high ionic concentrations used. Due to the stability issue of, sodium nitrite and sodium benzoate are being turned away from industry.

In aqueous surface-coating compositions treated according to the present invention, the corrosion inhibitor composition of the present invention alone or in combination with other additives such as known corrosion inhibitors,
It may be used as a mixture of biocides, emulsifiers and / or pigments.

Other corrosion inhibitors which can be used are, for example, the classes a), b), c) and d) indicated above.

Examples of biocides that can be used in these aqueous systems in addition to the corrosion inhibitor compositions of the present invention include: phenolics and alkylated and halogenated phenolics such as pentachlorophenol, o-
Phenylphenols, o-phenoxyphenols and chlorinated o-phenoxyphenols, and salicylanilides, diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.

Examples of pigments which can be used in these aqueous systems in addition to the corrosion inhibitor composition of the present invention are titanium dioxide, zinc yellow,
Organic pigments such as iron oxide and phthalocyanine.

[0051]

The invention is further described in the following examples. Examples 1 and 2 A) A corrosion inhibitor composition is formed by mixing 30 parts by weight of 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine and 20 parts by weight of anthranilic acid. To do. B) The corrosion inhibiting function of the composition A) is then evaluated by the DIN (German Industrial Standard) 51360 test ("filter tip test"). DI with triethanolamine and / or borax added so that the solution that produced composition A) was adjusted to pH 8.0 or 8.5.
It dissolves in water specified by N51360. The concentration of the corrosion inhibitor A) is 1.0 or 1.5% by weight, respectively. Rust from cast iron "chips" placed on filter paper and moistened with a small volume of test solution is evaluated according to the following rating rate. 0 no rust 2 rust traces 3 minor rust 4 moderate rust 5 severe rust The results obtained and 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine and anthranilic acid, The corresponding results obtained with each used alone are shown in Tables 1 and 2 below.

Example 3 A) A corrosion inhibitor composition is prepared by mixing 10 parts by weight of p-toluenesulfonamidocaproic acid and 10 parts by weight of anthranilic acid. B) The following results are obtained using the procedure described in Example 1 (B) at pH 8.5.

Example 4 A) Alox 232 (commercially available 11 carbon atoms)
/ 12 dicarboxylic acid mixture) and 10 parts by weight of anthranilic acid to prepare a corrosion inhibitor composition. B) The following results are obtained using the procedure described in Example 1 (B) at pH 8.5.

Example 5 A) 30 parts by weight of 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine and N'-
(2-Carboxybenzyl) -2-aminobenzoic acid 10
A corrosion inhibitor composition containing parts by weight is prepared. B) The following results are obtained using the procedure described in Example 1 (B) at pH 8.5. The results in Tables 1, 2, 3, 4 and 5 demonstrate a significant improvement in the corrosion inhibitor function of the compositions of this invention in the alkaline pH range.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C23F 11/16 8414-4K (72) Inventor Kevin Leslie Virtual UK, SK3 8SG, Stock Port, Devansport, Oakfield Road 50

Claims (20)

[Claims] 1. A corrosion inhibitor composition comprising: A) A1) the following formula I, based on the total weight thereof: {In the formula, Z represents an alkylene group having 1 to 11 carbon atoms, R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, and R ₃ is a group: —NR ₄ R ₅ [in the group R ₄
Is an alkyl group having 1 to 12 carbon atoms or a group: -Z
-COOH (in the group Z represents. The abovementioned meaning) represents an alkyl group having R ₅ is not hydrogen or C 1 -C and represents 12. ]] Is represented. } The triazine-carboxylic acid represented by these, or its water-soluble salt; A2) Formula II: (In the formula, R ₆ and R ₇ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m is an integer in the range of 1 to 10.) An acid or a water-soluble salt thereof; and A3) a dicarboxylic acid represented by formula III: HOOC- (CH ₂ ) _n -COOH III (wherein n represents an integer in the range of 4 to 12) or a mixture thereof, Or a water-soluble salt thereof; a carboxylic acid corrosion inhibitor consisting of one or more of, or 40 to 90% by weight of a water-soluble salt thereof; B) Formula IV: (In the formula, R ₈ is a hydrogen atom or the following formula V or VI Represents a group represented by. ) 1 of aminobenzoic acid represented by
10 or 60% by weight of one or more or one or more of its water-soluble salts; C) Formula VII: NR ₉ R ₁₀ R ₁₁ VII, wherein R ₉ , R ₁₀ and R ₁₁ are independent. And then a hydrogen atom,
Optionally represents a straight-chain or branched C 1 -C 12 alkyl group interrupted by an oxygen atom, or R ₉ , R ₁₀ and R ₁₁ are of the formula VIII: (In the formula, R ₁₂ and R _{13 each} independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and p and q each independently represent 0 or an integer in the range of 1 to 10. , In which p and q are not 0 at the same time, and R
_At least one of ₉ , R ₁₀ and R ₁₁ represents a group represented by the formula VIII. Corrosion inhibitor composition containing 0 to 10% by weight of an alkanolamine represented by the formula (4); and D) 0 to 10% by weight of an alkali metal borate. 2. A1) R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, and R ₃ is a group: —NR ₄ R
₅ (in the group, R ₄ represents an alkyl group having 1 to 8 carbon atoms or —Z—COOH, R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents 1 to 4 carbon atoms. 5 represents an alkylene group of 5)
Or a water-soluble salt thereof; A
2) is a compound represented by formula II in which R ₆ and R ₇ independently represent a hydrogen atom or a methyl group, or a water-soluble salt thereof; and A3) is a compound in which n is 11 or 12.
An acid represented by III, a mixture of an acid represented by formula III in which n is 11 and an acid represented by formula III in which n is 12, or a water-soluble salt thereof; Composition. 3. A1) is 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine or a water-soluble salt thereof; A2) is p-toluenesulfonamidocaproic acid or a salt thereof. A water-soluble salt; and A3) is an acid of formula III in which n is 11 and n is 1
A composition according to claim 1, which is a mixture of acids of formula III representing 2, or a water-soluble salt thereof. 4. The composition according to claim 2, wherein A) is A1). 5. The composition according to claim 2, wherein A) is A2). 6. The composition according to claim 2, wherein A) is A3). 7. The composition according to claim 3, wherein A) is A1). 8. The composition according to claim 3, wherein A) is A2). 9. The composition according to claim 3, wherein A) is A3). 10. B) is anthranilic acid, N-(2-carboxyethyl) -2 ¹ - aminobenzoic acid or composition according to claim 1 which is water-soluble salts thereof. 11. B) is anthranilic acid, N-(2-carboxyethyl) -2 ¹ - aminobenzoic acid or composition of claim 2 which is water-soluble salts thereof. 12. B) is anthranilic acid, N-(2-carboxyethyl) -2 ¹ - aminobenzoic acid or composition of claim 3 which is water-soluble salts thereof. 13. A composition according to claim 1, wherein an alkanolamine C) is present and it is triethanolamine. 14. A composition according to claim 2, wherein an alkanolamine C) is present and it is triethanolamine. 15. A composition according to claim 3, wherein an alkanolamine C) is present and it is triethanolamine. 16. The composition according to claim 1, wherein borate D) is present and it is sodium borate or potassium borate. 17. The composition according to claim 2, wherein the borate salt D) is present and it is sodium borate or potassium borate. 18. The composition according to claim 3, wherein the borate salt D) is present and it is sodium borate or potassium borate. 19. A method of inhibiting corrosion of ferrous metals in contact with an aqueous system comprising adding to the aqueous system an effective corrosion inhibiting amount of the composition of claim 1. 20. In the above composition, A) is 2,4,6-tris (5-carboxypentylamino) -1,3,5-
Triazine or a water-soluble salt thereof, or p-toluenesulfonamidocaproic acid or a water-soluble salt thereof, or a compound of the formula HOOC- (CH ₂ ) in which n is 11 and 12.
an acid or a water soluble salt represented by _n -COOH; and B) is anthranilic acid, N-(2-carboxyethyl) -2 ¹ - amino benzoic acid or its water-soluble salts, in claim 19 The method described.