MXPA97001088A

MXPA97001088A - Composition of corrosion inhibitor coating for meta

Info

Publication number: MXPA97001088A
Application number: MXPA/A/1997/001088A
Authority: MX
Inventors: Kramer Andreas; Wolf Jeanpierre; Braig Adalbert; Frey Markus
Original assignee: * Ciba Specialty Chemicals Holding Inc
Priority date: 1996-02-12
Filing date: 1997-02-12
Publication date: 1997-08-01

Abstract

A description is given of compounds of the formula: wherein the general symbols are as defined in claim 1, and of their salts of zirconium, bismuth, and calcium, and of the salts with the compounds of the formula II: Formula) wherein the general symbols are as defined in claim 1, as corrosion inhibitors in coating compositions for protecting metal surfaces

Description

COMPOSITION OF CORROSION INHIBITOR COATING FOR METALS The present invention relates to coating compositions comprising an organic film-forming binder, preferably a coating material, and certain aminophosphonic acids or aminophosphorous acids and / or their zirconium, bismuth and calcium salts, and salts thereof with certain amines, as corrosion inhibitors, to the use thereof in coating compositions for protecting metal surfaces, and to novel aminophosphonic acids and novel salts of aminophosphonic acids and aminophosphorous acids. The use of alkali metal, alkaline earth metal, transition metal, and amine salts, carboxylic acids and transition metal complexes of ketocarboxylic acids, as corrosion inhibitors in aqueous systems, is known and described , for example, in patents numbers US 4,909,987; EP-A-0,412,933; EP-A-0, 496, 555; EP-A-0, 554, 023 or EP-A-0, 619, 290. European Patent Number EP-A-0,437, 722 discloses certain amine oxides of phosphonic acids as corrosion inhibitors. U.S. Patent Number US 4,000,012 describes an effect of iron phosphate or zinc phosphate coatings on steel, the action of which is markedly improved by treatment with a solution of a-aminophosphonic acid or soluble salts in water of it. U.S. Patent Number US 4,076,501 relates to an effect against the corrosion of metals by means of diphosphonic acids. U.S. Patent No. 4,917,737 discloses a method for sealing a phosphate metal substrate using certain alkylaminodiphosphonic acids. U.S. Patent Number US 3,925,245 (German Patent Number DE-A-2, 231, 206) relates to a corrosion inhibiting composition for metal surfaces, which comprises inorganic nitriles and aminoalkylphosphonic acids. U.S. Patent Number US 3,837,803 (German Patent Number DE-A-2, 335, 331) refers to a corrosion inhibition process for metallic components that are in contact with aqueous systems, through the use of synergistic mixtures of water-soluble organophosphonic acids and their salts, a water-soluble orthophosphate, and calcium ions. U.S. Patent No. 3,483,133 relates to the use of certain aminomethylphosphonic acids as corrosion inhibitors for metals in aqueous systems. British Patent Number GB-A-1, 201, 334 in the same manner describes the use of certain phosphonic acids as corrosion inhibitors for metals in aqueous systems. British Patent Number GB-A-2, 121, 419 discloses the use of certain phosphonic acids as corrosion inhibitors in coating materials.

One of the objects of the invention, then, was to provide - specifically for coating systems, especially those which are water-based - a coating composition which, first, inhibited or completely eliminated the corrosion of metals and second, promoted good adhesion from the coating to the metal. It has been discovered that certain aminophosphonic acids or aminophosphorous acids and / or their zirconium, bismuth and calcium salts, and also the salts thereof with certain amines, surprisingly suppress the oxidation of metals, and at the same time greatly improve the adhesion of the metal. metal coating. These acids and salts are for the most part novel, and are particularly suitable in novel coating compositions, both as corrosion inhibitors and as adhesion promoters. Accordingly, the invention relates to coating compositions comprising: a) an organic film-forming binder, and b) as a corrosion inhibitor, ar) at least one compound of the formula I: where : R is alkyl of 4 to 12 carbon atoms substituted by hydroxyl, carboxyl, or amino; or R, and R5, together with the nitrogen atom to which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which I'm interrupted \ do by oxygen, sulfur, or Nf-R (/ R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or they are benzyl, R4 is hydroxyl, O II R5 is -CH-P-OH OH R6 is alkyl of 1 to 18 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, and m is 0 or 1; or ß) at least one salt derived from: i) a compound of the formula I ': wherein: R 'is hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 3 to 25 carbon atoms interrupted by oxygen, \ sulfur, or N ~ R7 > alkyl of 2 to 25 atoms carbon substituted by hydroxyl, carboxyl, or amino; alkenyl of 2 to 24 carbon atoms, cycloalkyl of 4 to 15 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl of 7 to 9 carbon atoms, or or R'j and R'5 together with the nitrogen atom to which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or that is interrupted by oxygen, sulfur, N-R6 R'4 is hydrogen, hydroxyl, or -0Ra, R's is hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 3 to 25 carbon atoms interrupted by oxygen, Sulfur, or I N-R7; / alkenyl from 2 to 24 carbon atoms, cycloalkyl of 4 to 15 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl of 7 to 9 carbon atoms, or O II -CH2-P-OH, R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R1 is alkyl of 1 to 6 carbon atoms, cycloalkyl of 4 to 15 carbon atoms, or phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; and with the proviso that, if R'x or R's is hydrogen, it is 0; and ii) an amine of formula II wherein: RH and Ri5"independently of each other, are hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur; phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, alkenyl of 3 to 24 carbon atoms or -x-Si; or Rl4 and R13, together with the nitrogen atoms with which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen, sulfur, or N-R7; / R16 is alkyl of 1 to 25 carbon atoms, alkyl of 2 to 25 carbon atoms which is interrupted by oxygen or sulfur, - hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkenyl of 2 to 24 carbon atoms, R17 is hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkoxy of 2 to 18 carbon atoms which is interrupted by oxygen or sulfur; and if b is 0, three radicals R17 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 18 carbon atoms, alkylidene of 2 to 20 carbon atoms, phenylalkylidene of 7 to 20 atoms carbon, cycloalkylene of 5 to 8 carbon atoms, phenylene or naphthylene unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or is alkylene of 4 to 18 carbon atoms which is interrupted by oxygen, sulfur, or N-R,, with the condition that they never join / atoms of nitrogen at the same carbon atoms, a is l or 2, b is 0, 1, or 2, and if a is 1, x is hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 2 to 24 atoms of carbon substituted by hydroxyl, alkyl of 3 to 25 carbon atoms which is interrupted by oxygen or sulfur; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, - alkenyl of 3 to 24 carbon atoms, if a is 2, (R,? R18 is - s¡ -; V with the proviso that, (^ b if in the compound of the formula I ', R', is alkyl of 1 to 12 O carbon atoms, II -CH-P-OH 2 I OH O or 2-hydroxyethyl, R'5 is -CH, -P-OH 2 I OH R2 and R3 are hydrogen, R'4 is hydroxyl, and is 0, and if in the compound of formula IIa is 1 and X is a direct bond, then at least one of the radicals R14, R15, and R, 8 it is different from hydrogen; or iii) zirconium, bismuth, or calcium.1 Alkyl of 2 to 25 carbon atoms substituted by hydroxyl, carboxyl, or amino, is a branched or unbranched radical preferably containing from 1 to 3, in particular 1 or 2 groups hydroxyl, carboxyl, or amino, such as, for example, hydroxyethyl, carboxyethyl, aminoethyl, 3-hydroxypropyl, 3-carboxypropyl, 3-aminopropyl, 2-hydroxypropyl, 2-carboxypropyl, 2-aminopropyl, 4-hydroxybutyl, -carboxibuyl, 4-aminobutyl, 3-hydroxybutyl, 3-carboxybutyl, 3-aminobutyl, 2-hydroxybutyl, 2-carboxybuyl, 2-aminobutyl, 5-hydroxypentyl, 5-carboxypentyl, 5-aminopentyl, 4-hydroxypentyl , 4-carboxypentyl, 4-aminopentyl, 3-hydroxypentyl, 3-carboxypentyl-lo, 3-aminopentyl, 2-hydroxypentyl, 2-carboxypentyl, 2-aminopentyl, 6-hydroxyhexyl, 6-carboxyhexyl, 6-aminohexyl, 5-hydroxyhexyl , 5-carboxyhexyl, 5-aminohexyl, 4-hydroxyhexyl, 4-carboxyhexyl, 4-aminohexyl, 3-hydroxyhexyl, 3-carboxyhexyl, 3-aminohexyl, 2-hydroxyhexyl it, 2-carboxyhexyl, 2-aminohexyl, 7-hydroxyheptyl, 7-carboxyheptyl, 7-aminoheptyl, 6-hydroxyheptyl, 6-carboxyheptyl, 6-aminoheptyl, 5-hydroxyheptyl, 5-carboxyheptyl, 5-aminoheptyl, 4- hydroxyheptyl, 4-carboxyheptyl, 4-aminoheptyl, 3-hydroxyheptyl, 3-carboxyheptyl, 3-a-hydroxyheptyl, 2-hydroxyheptyl, 2-carboxyheptyl, 2-aminoheptyl, 8-hydroxyoctyl, 8-carboxy octyl, 8-aminooctyl, -hydroxyoctyl, 7-carboxyoctyl, 7-aminooctyl, 6-hydroxyoctyl, 6-carboxyoctyl, 6-aminooctyl, 5-hydroxyoctyl, 5-carboxyoctyl, 5-aminooctyl, 4-hydroxyoctyl, 4-carboxyoctyl, 4-aminooctyl, 3-hydroxyoctyl , 3-carboxyoctyl, 3-aminooctyl, 2-hydroxyoctyl, 2-carboxyoctyl, 2-aminooctyl, 9-hydroxynonyl, 9-carboxinonyl, 9-aminononyl, 10-hydroxydecyl, 10-carboxycyl, 10-aminodecyl, 11-hydroxyun-decyl , 11-carboxyundecyl, 11-aminoundecyl, 12-hydroxydecyl, 12-carboxydecyl, 12-aminododecyl, 13-hydroxytridecyl, 13-carboxytridecyl, 13-aminotridecyl, 14-hydroxytetradecyl, 14-ca rboxitetradecyl, 14-aminotetradecyl, 15-hydroxypentadecyl, 15-carboxypentadecyl, 15-aminopentadecyl, 16-hydroxyhexadecyl, 16-carboxyhexadecyl, 16-aminohexadecyl, 17-hydroxyheptadecyl, 17-carboxyheptadecyl, 17-aminoheptadecyl, 18-hydroxyoctadecyl, 18-carboxyoctadecyl, 18-aminooctadecyl, 20-hydroxyeicosyl, 20-carboxieicosilo, 20-aminoeicosilo, 22-hidroxidocosilo, 22-carboxidocosilo or 22-aminodocosilo. A preferred definition of Rj is alkyl of 4 to 12 carbon atoms, substituted by hydroxyl, carboxyl, or amino, especially alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl, for example alkyl of 5 to 12 carbon atoms, substituted by hydroxyl or carboxyl. A particularly preferred definition of Rj is alkyl of 5 to 10 carbon atoms substituted by hydroxyl or carboxyl, especially alkyl of 5 to 8 carbon atoms substituted by hydroxyl or carboxyl, for example alkyl of 5 to 6 carbon atoms substituted by hydroxyl. An especially preferred definition of Rj is 5-hydroxypentyl. A preferred definition of R'j is alkyl of 2 to 20 carbon atoms substituted by hydroxyl, carboxyl, or amino, especially alkyl of 5 to 20 carbon atoms substituted by hydroxyl, carboxyl, or amino, for example alkyl of 5 to 12 carbon atoms substituted by hydroxyl, carboxyl, or amino. A particularly preferred definition of R'j is alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl, especially alkyl of 5 to 11 carbon atoms substituted by hydroxy or carboxyl, for example, 5-hydroxypentyl or 11-carboxyundeyl. A particularly preferred definition of R "j is alkyl of 4 to 14 carbon atoms substituted by hydroxyl, carboxyl, or amino, especially alkyl of 5 to 14 carbon atoms substituted by hydroxyl or carboxyl, for example alkyl of 5 to 11 carbon atoms. carbon substituted by hydroxyl or carboxyl One of the preferred definitions Rj4, Rl5, and R18 (if a = 1) is alkyl of 2 to 24 carbon atoms substituted by hydroxyl, especially alkyl of 2 to 20 carbon atoms substituted by hydroxyl, for example, alkyl of 2 to 14 carbon atoms substituted by hydroxyl A particularly preferred definition R14, R15, and R18 is alkyl of 2 to 12 carbon atoms substituted by hydroxyl, especially alkyl of 2 to 8 carbon atoms substituted by hydroxyl, for example, alkyl of 2 to 4 carbon atoms substituted by hydroxy, such as 2-hydroxyethyl, for example, wherein R, and R5, or R ', and R * 5, or R ", and R" 5, or R , and R, along with the nitrogen atom co where they are attached, they form a 5-, 6-, or 7-membered heterocyclic ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen, sulfur, or N_R / 6 ' this denotes, for example, the following radicals: H3C OR N-. O N-, HN N-, H3C-N N. H3C RH Ri5 &preferably form, with the nitrogen atom to which they are attached, a 6-membered heterocyclic ring interrupted by oxygen, such as, by example, OR N-.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical such as, for example, methyl, ethyl, propyl, isopropyl, normal butyl, secondary butyl, isobutyl, tertiary butyl, 2-ethylbutyl, normal pentyl, isopentyl, -methylpentyl, 1,3-dimethylbutyl, normal hexyl, 1-methylhexyl, normal hepyl, isoheptyl, 1, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, normal octyl, 2-ethylhexyl, 1 , 1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1, 1,3,3,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl , heptadecyl, octadecyl, eicosyl or docosyl. A preferred definition of R2 and R3 is alkyl of 1 to 20 carbon atoms, especially alkyl of 1 to 12 carbon atoms, for example alkyl of 1 to 8 carbon atoms. A particularly preferred definition of R2 and R3 is alkyl of 1 to 6 carbon atoms, especially alkyl of 1 to 4 carbon atoms, for example methyl. A preferred definition of R ^ is alkyl of 1 to 18 carbon atoms, especially alkyl of 1 to 12 carbon atoms, for example alkyl of 1 to 8 carbon atoms. A particularly preferred definition of R6 is alkyl of 1 to 6 carbon atoms, especially alkyl of 1 to 4 carbon atoms, for example methyl or ethyl. A preferred definition of R * j and R'5 is alkyl of 1 to 25 carbon atoms, especially alkyl of 5 to 20 carbon atoms, for example alkyl of 5 to 18 carbon atoms. A preferred definition of R "? And R" 5 is alkyl of 8 to 14 carbon atoms. A preferred definition of R7 is alkyl of 1 to 6 carbon atoms, especially alkyl of 1 to 4 carbon atoms, for example methyl. A preferred definition of R8 is alkyl of 1 to 6 carbon atoms, especially alkyl of 1 to 4 carbon atoms, for example methyl or ethyl. A preferred definition of R14, R15, R16, and Rjg is alkyl of 1 to 20 carbon atoms, especially alkyl of 1 to 14 carbon atoms, for example alkyl of 1 to 12 carbon atoms. A particularly preferred definition of R 14, R 5, R 16, and R 18 is alkyl of 1 to 8 carbon atoms especially alkyl of 1 to 4 carbon atoms, for example methyl or ethyl.

Cycloalkyl of 4 to 15 carbon atoms is, for example, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, or cyclopentadecyl. A preferred definition of R'j, R2, R3, R * 5 and R8 is cycloalkyl of 5 to 8 carbon atoms, especially cycloalkyl of 6 to 7 carbon atoms, for example cyclohexyl. Phenyl substituted by alkyl of 1 to 4 carbon atoms preferably containing 1 to 3, in particular 1 or 2 alkyl groups, is, for example, o-, m-, or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethyl-phenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenol, 4-tertiary butyl-phenyl, 2 -ethylphenyl, or 2,6-diethylphenyl. Phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or substituted on the phenyl radical by 1 to 3 alkyl groups of 1 to 4 carbon atoms is, for example, benzyl, or-ethylbenzyl, OI, Qf-dimethylbenzyl , 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethyl-benzyl, 2,6-dimethylbenzyl, or tertiary-4-butyl-benzyl. Benzyl is preferred. Alkylate of 3 to 25 carbon atoms that is interrupted I ask for oxygen, sulfur, or / N R7 is, for example, CH3-0-CH2CH2-, CH3-S-CH2CH2-, CH3-NHCH2CH2-, CH, - N (CH3) CH2CH2-, CH3-0-CH2CH2- 0-CH2CH2-, CH3- (0-CH2CH2-) 20-CH2CH2-, CH3- (O-CH2CH2-) 30-CHJCHJ or CH3- (O-CH2CH2-) 40-CH2-. Alkenyl having from 2 to 24 carbon atomsis a branched or unbranched radical, such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl , n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having from 3 to 18, especially from 3 to 12, for example from 3 to 6, especially from 3 to 4 carbon atoms. Alkoxy having up to 18 carbon atoms is a branched or unbranched radical, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, normal butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetrade- Ciloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having from 1 to 12, especially from 1 to 8, for example from 1 to 6 carbon atoms. Alkoxy of 2 to 18 carbon atoms interrupted by oxygen or sulfur is, for example, CH3-0-CH2-, CH3-S-CH2-, CH3-0-CH2CH20-, CH3-S-CH2CH20-, CH3-0- (CH2) 2-0- (CH2) 2-0-, CH3- (0-CH2CH2-) 20-CH2CH20-, CH3- (0-CH2CH2-) 30-CH2CH20- or CH3- (0-CH2CH2-) -CH2CHp-. Alkylene of 1 to 18 carbon atoms is a branched or unbranched radical, such as, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, or octadecamethylene. Preference is given to alkylene of 1 to 12 carbon atoms, especially alkylene of 1 to 8 carbon atoms. Alkylidene having from 2 to 20 carbon atoms is, for example, ethylidene, propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethyl pentylidene. Alkylidene of 2 to 8 carbon atoms is preferred. Phenylalkylidene having 7 to 20 carbon atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Phenylalkylidene of 7 to 9 carbon atoms is preferred. Cycloalkylene of 5 to 8 carbon atoms is a saturated hydrocarbon group having 2 free valencies, and at least one ring unit, and is, for example, cyclopentylene, cyclohexylene, cycloheptylene, or cyclooctylene. Cyclohexylene is preferred. Phenylene or unsubstituted naphthylene or substituted by alkyl of 1 to 4 carbon atoms, is, for example, 1,2-, 1,3- or 1,4-phenylene, or 1,2-, 1,3-, 1, 4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-phenylene is preferred. Alkylene with 4 to 18 carbon atoms interrupted by oxygen, sulfur, or /, N ~ R? is, for example, -CH2CH2-O-CH2CH2-, -CH2CH2- S-CH2CH2-, CH2CH2-NH-CH2CH2-, -CH2CH2-N (CH3) -CH2CH2-, -CH2CH2-0-CH2CH2-0-CH2CH2-, - (CH2) 2- (0-CH2CH2-) 20- (CH2) 2-, - (CH2) 2- ( 0-CH2CH2-) 30- (CH2) 2-, - (CH2) 2- (0-CH2CH2-) 40- (CH2) 2 or -CH2CH2-S-CH2CH2-. Particular mention should be made to coating compositions comprising, as component (b), at least one compound of formula I or a salt derived from: i) a compound of formula I ', and ii) an amine of formula II, wherein R2 and R3 are hydrogen. Convenient coating compositions are those which comprise as component (b), at least one compound of formula I wherein Rj is alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl. Preference is given to coating compositions comprising, as component (b), at least one salt derived from: i) a compound of formula I ', and ii) an amine of formula II wherein: R1 is alkyl of 5 to 18 carbon atoms, or alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl; R'4 is hydrogen or hydroxyl, and R'j is alkyl of 5 to 25 carbon atoms, or -CH-P- • OH R ', Preference is also given to coating compositions comprising, as component (b), at least one salt derived from: i) a compound of formula I', and ii ) an amine of formula II, wherein: i4 and Ri5 independent of one another, are hydrogen, alkyl of 1 to 8 carbon atoms, or alkyl of 2 to 14 carbon atoms substituted by hydroxyl; or Rj4 and R15, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and R18 is alkyl of 1 to 14 carbon atoms, alkyl of 2 to 14 carbon atoms substituted by hydroxyl; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or it is benzyl. Also of interest are coating compositions comprising, as component (b), at least one compound of formula I, or a salt derived from: i) a compound of formula I1, and ii) an amine of Formula II, wherein: Rj is alkyl of 5 to 12 carbon atoms substituted by hydroxyl, carboxyl, or amino; or R, and R5, together with the nitrogen atom to which they are attached, form a 5, 6, or 7-membered heterocyclic ring that is interrupted by oxygen, sulfur ÓN-R6 R'i is alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms which is interrupted by oxygen, sulfur, or \ N-R7 alkyl of 5 to 20 carbon atoms substituted by hydroxyl, carboxyl, or amino; alkenyl of 5 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or II carbon; benzyl or -C- -P-OH R'i and R'5, together I I R'_ with the nitrogen atom to which they are attached, they form a 6-membered heterocyclic ring, which is unsubstituted or is substituted by alkyl of 1 to 4 carbon atoms or is \ interrupted by oxygen, sulfur, or N-R, R2 and R3"independently of each other, are hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl; R4 is hydroxyl, R'4 is hydrogen, hydroxyl, or -OR8, R5 is -CH2-P-OH. OH R'5 is hydrogen, alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms which is interrupted by oxygen, sulfur, or N-R7; alkenyl from 5 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; benzyl, or OR II -CH-P-OH, R6 is alkyl of 1 to 12 carbon atoms or benzyl, m is 0 or 1, R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R8 is alkyl of 1 to 6 carbon atoms, cyclohexyl, or phenyl, R14 and R5, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms substituted by hydroxyl , alkyl of 3 to 20 carbon atoms interrupted by oxygen or sulfur, - phenylalkyl of 7 to 9 carbon atoms, - alkenyl of 3 to 20 carbon atoms, or or R14 and Rj5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring, which is \ interrupted by oxygen, sulfur, or N-R7 R16 is alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 20 carbon atoms, R17 is hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkoxy of 2 to 12 carbon atoms interrupted by oxygen or sulfur; and b is 0, three RI7 radicals are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, phenylalkylidene of 7 to 12 carbon atoms , cyclohexylene of 5 to 8 carbon atoms, phenylene, naphthylene, or alkylene of 4 to 18 carbon atoms interrupted by oxygen or sulfur, with the proviso that two nitrogen atoms never join the same carbon atom. a is 1 or 2, b is 0, 1, or 2, and if a is 1, R18 is hydrogen, alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms substituted by hydroxyl, alkyl of 3 to 20 carbon atoms interrupted by oxygen or sulfur; phenyl, phenylalkyl of 7 to 9 carbon atoms, alkenyl of 3 to 20 carbon atoms, if a is 2, (R,? R18 is - There is a particular interest in coating compositions comprising, as component (b) at least one compound of formula I, or a salt derived from i) a compound of formula I1, and ii) an amine of the formula II, wherein: Rj is alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; or R, and R5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur. R "is alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms interrupted by oxygen or sulfur; alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; alkenyl of 5 to 10 carbon atoms, cyclohexyl, phenyl, or benzyl, or R ', and R'5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur. R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, or benzyl, R4 is hydroxyl, R'4 is hydrogen or hydroxyl, R5 is -CH-P-OH, OH R's is alkyl of 5 to 20 carbon atoms, alkyl of to 20 carbon atoms interrupted by oxygen or sulfur, -alkenyl of 5 to 20 carbon atoms, cyclohexyl, phenyl, benzyl, or _CH •? _p_-0H R4 m is 0, R 14 and R 5, independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen or sulfur, - benzyl, alkenyl of 3 to 12 carbon atoms, or -X-Si (Ru) 3b or Rj4 and Rjj, together with the nitrogen atom with which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur; R 16 is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms, R 7 it is hydroxyl or alkoxy of 1 to 12 carbon atoms; and if b is 0, three radicals R17 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 8 carbon atoms, cyclohexylene, phenylene, naphthylene, or is alkylene of 4 to 12 carbon atoms interrupted by oxygen, with the proviso that two nitrogen atoms never join the same carbon atom, a is 1 or 2, b is 0, l, or 2, and if a is 1, Rj8 is hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen, -phenyl, benzyl, alkenyl of 3 to 12 carbon atoms or if a is 2, (R, R, 8 is -Si- Coating compositions that are especially of particular interest are those which comprise, as component b), at least one compound of formula I, or a salt derived from: i) a compound of the formula I ', and ii) an amine of the formula II, wherein: Rj is alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl, R'i is alkyl of 5 to 18 carbon atoms; carbon, or alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; R2 is hydrogen, R3 is hydrogen, R4 is hydroxyl, R'4 is hydrogen or hydroxyl, R5 is -CH-P-OH, I OH R'5 is alkyl of 5 to 18 carbon atoms or O II -CH2-P-OH, 2 I R "4 m is 0, Rj4 and Rj5, independently of one another, are hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or R14 and R, 5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and RJ8 is alkyl of 1 to 4 carbon atoms. carbon, alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or is phenyl. Examples of the particularly preferred amines of formula II are n-butyl amine, isobutyl amine, terbutyl amine, n- / iso- / teramyl amine, n-hexyl amine, n-heptylic amine, n-octyl amine, isooctyl amine, amine teroctylyl, n-nonyl amine, decyl amine, n-dodecyl amine, isododeclic amine, terdodeclic amine, n-tridecyl amine, isotridecyl amine, tertridecyl amine, n-tetradecyl amine, isotetradeclic amine, tertetradecyl amine, n-amine octadecyl, isooctadecyl amine, teroctadecyl amine, n-nonadeclic amine, isononadeclic amine, ternonadeclic amine, n-eicosamine, isoeicosamine, tereicosamine, n-heneicosamine, isoheneicosamine, terheneicosamine, n-docosamine, isodocosamine, terdocosamine, n-tricosamine, isotricosamine , tertricosamine, n-tetracosamine, isotetracosamine, tertetracosamine, benzyl amine, dibenzyl amine, N-benzyl aniline, di-n-butyl amine, diisobutyl amine, amine diisodecyl, ditrideclic amine, diisooctyl amine, dithyroctyl amine, diisotetradecyl amine, di-n-octadeclic amine, diterbutyl amine, di-n-octyl amine, di-2-ethylhexyl amine, di-n-dodecyl amine, di-n-di n-eicosilic, di-n-tetraeicosilic amine, 3-butoxypropyl amine, hexoxybutyl amine, nonyloxypropyl amine, aniline, N-methyl aniline, N-ethyl aniline, N, N-dimethyl aniline, tri-n-butyl amine, triisobutyl amine, tri-n-octyl amine, and in particular ethanolic amine, N, N-dimethylaminoethanol, tris (hydroxymethyl) -aminomethane (TRISAMINO), 2-amino-2-ethyl-l, 3-propane-diol ( AEPD), 2-amino-2-methyl-1-propanol (AMP 95), 2-dimethylamino-2-methyl-1-propanol (DMAMP 80), 2-amino-2-methyl-1,3-propanediol, morpholine N-methyl, N-ethyl morpholine, triethanolic amine, triethyl amine, ammonia, 3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N-allyl-3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, N, N'-dimethyl-3-aminopropylethexysilane, N, N'-dibutyl-3-aminopropyltriethoxysilane, N, N '- (di-2-hydroxyethyl) -3-aminopropyltriethoxysilane, bis- [3- (triethoxysilyl) -propyl amine], 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3- (6-aminohexylamino) propyltrimethoxysilane, 3- [ 2- (2-aminoethylamino) ethylamino] -propyltrimethoxysilane, aminophenyltrimethoxysilane and 3-aminopropyltriethoxysilane. A particular preference is given to N-ethyl morpholine, N, N-dimethyl aniline, trietanolic amine, dietanolic amine, triethyl amine, ammonia, 3-aminopropyltri-methoxysilane, and 3-aminopropyltriethoxysilane. Some of the compounds of the formulas I and I * are known in the literature, - others can be prepared in a manner analogous to British Patent Number GB-A-2, 121,419; K. Moedrit-zer et al., J. Org. Chem. _1, 1603-1607 (1966), - Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], volume XII / 1, pages 483-489 (1963); or volume E2, 302-304 (1982). The compounds of the formula II, especially the aminosilanes, are known in the literature, or can be prepared in analogy to J.L. Speier et al., J.Org. Chem 3_ £ (21), 3120-3126 (1971); L-Birkofer et al., Chapter 10, pages 655 to 751 in S. Palai, Z. Pappoport "The Chemistry of Organic Silicon Compounds," John Wiley & Sons Ltd., 1989; or E.P. Plueddeman, "Silane Coupling Agents", Plenum Press 1982, pages 1-233.

It is also possible to use mixtures of two or more different amines of the formula II to prepare the salts. The salts derived from: i) a compound of the formula I ', and ii) an amine of the formula II, or iii) zirconium, bismuth, or calcium, are conveniently prepared at the site in the course of the formulation of the coating composition. Accordingly, the present invention relates to coating compositions comprising: (a ') a film-forming organic binder (b') at least one acid of the formula I ', and (C) at least one amine of the formula II, or a compound of zirconium, bismuth, or calcium. The present invention also relates to a process for the preparation of a coating composition comprising, as the component (b) at least one compound of the formula I, or a salt derived from - i) a compound of the formula I ', and ii) an amine of formula II, or iii) zirconium, bismuth, or calcium, which comprises mixing an organic film-forming binder with component (b). The coating composition is preferably a coating material, especially an aqueous coating material. Examples of coating materials are lacquers, paints, or varnishes. These always contain an organic film-forming binder in addition to other optional components.

Preferred organic film-forming binders are epoxy resins, polyurethane resins, amino resins, acrylic resins, acrylic copolymer resins, polyvinyl resins, phenolic resins, styrene / butadiene copolymer resins, vinyl / acrylic copolymer resins, resins of polyester or alkyd resins, or a mixture of two or more of these resins, or a basic aqueous or acid dispersion of these resins or mixtures of these resins, or an aqueous emulsion of these resins or mixtures of these resins. Of particular interest are organic film-forming binders for aqueous coating compositions, such as, for example, alkyd resins; acrylic resins, epoxy resins of two components; polyurethane resins; polyester resins, which are normally saturated, phenolic resins which are dilutable in water or dispersions, water-dilutable urea resins, vinyl / acrylic copolymer-based resins; and hybrid systems based on, for example, epoxy acrylates. More specifically, the alkyd resins can be water-dilutable alkyd resin systems which can be used in the form of air drying, or in the form of furnace systems, optionally in combination with water-dilutable melamine resins systems can also be drying by oxidation, air drying, or furnace systems, which are optionally employed in combination with aqueous dispersions based on acrylic resins or copolymers thereof, with vinyl acetates, and so on. The acrylic resins can be pure acrylic resins, hybrid epoxy acrylate systems, copolymers of acrylic acid or acrylic ester, combinations with vinyl resins, or copolymers with vinyl monomers, such as vinyl acetate, styrene, or butadiene. These systems can be air drying systems or baking systems. In combination with appropriate polyamine crosslinkers, water-dilutable epoxy resins exhibit excellent mechanical and chemical resistance. If liquid epoxy resins are used, the addition of organic solvents to the aqueous systems can be omitted. The use of solid resins or dispersions of solid resins usually requires the addition of small amounts of solvent, in order to improve film formation. Preferred epoxy resins are those based on aromatic polyols, especially those based on bisphenols. Epoxy resins are used in combination with crosslinkers. The latter in particular may be functional amino or hydroxy compounds, an acid, an acid anhydride, or a Lewis acid. Examples thereof are polyamines, polyaminoamides, polymers based on polysulfide, polyphenols, boron fluorides and their complex compounds, polycarboxylic acids, 1,2-dicarboxylic anhydrides, or pyromellitic dianhydride.

The polyurethane resins are derived from polyethers, polyesters, and polybutadienes with terminal hydroxyl groups, on the one hand, and from aliphatic or aromatic polyisocyanates, on the other hand. Examples of suitable polyvinyl resins are polyvinyl butyral, polyvinyl acetate, or copolymers thereof. Suitable phenolic resins are synthetic resins in the course of which construction phenols are the main component, namely, in particular phenol-, cresol-, xylene-, and resorcinol-formaldehyde resins, alkylphenolic resins, and phenol condensation products with acetaldehyde, furfurol, acrolein, or other aldehydes. Also of interest are modified phenolic resins. The coating compositions may additionally comprise one or more components taken, for example, from the group consisting of pigments, dyes, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters, antioxidants, light stabilizers. , and curing catalysts. They may also include other known anti-corrosion agents, for example anti-corrosion pigments, such as pigments containing phosphate or borate, or metal oxide pigments or other organic or inorganic corrosion inhibitors, for example salts of nitroisophthalic acid, phosphoric esters, technical grade amines, or substituted benzotriazoles. The pigments are, for example, titanium dioxide, iron oxide, aluminum bronze, or phthalocyanine blue. Examples of fillers are talc, alumina, aluminum silicate, barites, mica, and silica. Corrosion inhibitors can be applied to a support material. Fillers or powder pigments are particularly suitable for this purpose. Flow control agents and thixotropic agents are based, for example, on modified bentonites. The adhesion promoters are based, for example, on modified silanes. It is also convenient to add fillers or basic pigments, which in particular binding systems give rise to a synergistic effect on the inhibition of corrosion. Examples of these basic fillers and pigments are calcium carbonate or magnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, alumina, aluminum phosphate, or mixtures thereof. Examples of basic organic pigments are those based on aminoanthraquinone. The corrosion inhibitors can be added to the coating material during their preparation, for example, during the pigment dispersion by milling, or the inhibitor is dissolved in a solvent, and then the solution is stirred in the coating composition. Solutions, especially aqueous solutions, of corrosion inhibitors can also be used to pretreat the metal surface, which can then be subsequently coated with a topcoat. In the preparation of the film-forming organic binder by addition polymerization or condensation polymerization of monomers, the corrosion inhibitors can be mixed in solid form, or can be dissolved with the monomers, even before the polymerization reaction. The novel compounds of the formula I, or the salts derived from: i) a compound of the formula I ', and ii) an amine of the formula II, or iii) zirconium, bismuth, or calcium, are conveniently used in an amount of 0.01 to 20 weight percent, preferably 0.05 to 5 weight percent, in particular 0.1 to 5 weight percent, based on the weight of the total solids content of the coating composition. The coating materials can be applied to the substrate by customary techniques, for example, by spraying, dipping, spreading, or electrodepositioning. In many cases, a plurality of layers are applied. Corrosion inhibitors are added primarily to the base layer (primer), since they are active in particular in the metal / coating interface. However, they can also be added to the middle layer or top layer as well. Depending on whether the binder is a physical, chemical, or oxidation drying resin, or a heat-curing or radiation-curing resin, the coating is cured at room temperature or by heating (baking) or by irradiation. The coating material is preferably a preparer for metal surfaces such as, for example, iron, steel, copper, zinc, or aluminum, and alloys thereof. In addition to the anticorrosive effect, the compounds of the formula I, or the salts derived from: i) a compound of the formula I ', and ii) an amine of the formula II, or iii) zirconium, bismuth, or calcium , have the advantage that they affect in a favorable manner the adhesion between the coating and the metal, show no adverse effects on the storage stability of the novel coating compositions, and exhibit good compatibility with the binder. A preferred embodiment of the invention, therefore, is the use of the compounds of the formula I, or salts derived from: i) the compounds of the formula I1, and ii) amines of the formulas II, or iii) zirconium , bismuth, or calcium, as corrosion inhibitors in coating compositions for metal surfaces. The present invention also relates to a process for the protection of a corrodable metal substrate, which comprises applying thereto a coating composition comprising, as component (a), an organic film-forming binder, and as the component (b), at least one compound of the formula I, or at least one salt derived from: i) a compound of the formula I ', and ii) an amine of the formula II or iii) zirconium, bismuth or calcium , and then drying and / or curing the coating composition. In the same way, the present invention relates to a process for the preparation of a corrosion-resistant surface coating on a corrodable metal surface, which comprises treating this surface with a coating composition comprising, as the component (a), an organic film formadpr binder, and component (b), at least one compound of formula I, or at least one salt derived from: i) a compound of formula I1, and ii) a amine of formula II or iii) zirconium, bismuth, or calcium, and then drying and / or curing the coating composition. Moreover, the present invention relates to a process for pretreating metal surfaces, which comprises applying to the metal surface an aqueous solution of a component (b) comprising at least one compound of the formula I or at least one salt from: i) a compound of the formula I ', and ii) an amine of the formula II or iii) zirconium, bismuth, or calcium, and drying it. The invention also relates to novel compounds of the formula I: (?) "R2 OR II R, -N- C- -p- -OH (I) I I Rs R3 R4 wherein: Rj is alkyl of 4 to 12 carbon atoms substituted by hydroxyl or amino; or R, and R5, together with the nitrogen atom to which they are attached, are a 5-, 6-, or 7-membered heterocyclic ring, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen, sulfur, or N-R6 R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or benzyl, R4 is hydroxyl, O II R5 is _CH-P-OH, 2 I OH R6 is alkyl of 1 to 18 carbon atoms, or phenylalkyl of 7 to 9 carbon atoms, and m is 0 or 1; and with the proviso that the compound of formula III is excluded: (III) The preferred groups of the novel compounds of the formula I correspond to the preferences expressed above for the coating compositions. Moreover, preference is given to compounds of the formula I wherein: Rj is alkyl of 5 to 11 carbon atoms substituted by hydroxyl; or R, and R5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 4 atoms carbon, cyclohexyl, phenyl, or benzyl, R4 is hydroxyl, Rs is -CH-P-OH, I OH m is 0. Also of interest are compounds of formula I wherein: Rj is alkyl of 5 to 8 carbon atoms substituted by hydroxyl, R2 is hydrogen, R3 is hydrogen, R4 is hydroxyl, OR Rs is _CH P_OH, > and 2 I OH m is 0. The invention further relates to novel salts derived from: i) a compound of the formula I ": where: R'1! is alkyl of 8 to 14 carbon atoms, alkyl of 4 to 14 carbon atoms substituted by hydroxyl, carboxyl, or Not me; alkenyl of 8 to 14 carbon atoms, or, or R "j and R" 5, together with the nitrogen atom with which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or substituted by alkyl of 1 to 4 atoms carbon, or that is interrupted by oxygen, sulfur or N-R6 '• R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or are benzyl, R "4 is hydrogen or hydroxyl, R" 5 is hydrogen, alkyl of 8 to 14 carbon atoms, alkenyl of 2 to 24 carbon atoms, or -CH-P-OH, R6 is alkyl of 1 to 18 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, and m is 0 or 1; with the proviso that, if R ", or R" 5 is hydrogen, is 0; and ii) an amine of formula II: wherein: R 4 and R 5, independently of one another, are hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur, - phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, - alkenyl of 3 to 24 carbon atoms or -x-5¡ or R14 and R15, together with the nitrogen atoms with which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen, sulfur, \ N-R7 R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R] 6 is alkyl of 1 to 25 carbon atoms, alkyl of 2 to 25 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkenyl of 2 to 24 carbon atoms, R, 7 is hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkoxy of 2 to 18 carbon atoms interrupted by oxygen or sulfur; and if b is O, three radicals R, 7 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 18 carbon atoms, alkylidene of 2 to 20 carbon atoms, phenylalkylidene of 7 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, phenylene or unsubstituted naphthylene or substituted by alkyl from 1 to 4 carbon atoms; or alkylene of 4 to 18 atoms of carbon that is interrupted by oxygen, sulfur, or N-R / 7 ' with the proviso that two nitrogen atoms never join the same carbon atoms, a is 1 or 2, b is 0, 1, or 2, and if a is l, Rj8 is hydrogen, alkyl of 1 to 25 atoms carbon, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms; alkenyl of 3 to 24 carbon atoms, if a is 2, (R «) b Rj8 is -si-; and with the proviso that, I (^ - the compound of formula II is not ammonia, trietanolic amine, or ethyl amine, or iii) zirconium, bismuth, or calcium. The preferred groups of novel salts correspond to the preferences expressed above for the coating compositions. Moreover, preference is given to salts derived from: i) a compound of the formula I ", and ii) an amine of the formula II, or iii) zirconium, bismuth, or calcium, wherein: R" j is alkyl of 8 to 14 carbon atoms, alkyl of 5 to 14 carbon atoms substituted by hydroxyl or carboxyl; or is alkenyl of 8 to 12 carbon atoms, or R "j and R" 5, together with the nitrogen atom with which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - R2 and R3, independently one of the other, they are hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, or benzyl, R "4 is hydrogen or hydroxyl, R" 5 is alkyl of 8 to 14 carbon atoms, alkenyl O of 5 to 20 carbon atoms, or -? C1H1? '' P? -? r? "or" • R "4 m is O, Ri4 and Ri5 'independently of each other, are hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2, to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen or sulfur; benzyl, alkenyl 3 to 12 carbon atoms, or x S; or Rj4 and R15, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - R16 is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms interrupted by oxygen or sulfur; hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms, Rj7 is hydroxyl or alkoxy of 1 to 12 carbon atoms, and if b is 0, three radicals Rj7 are together N (CH2CH20- ) 3, X is a direct bond, alkylene of 1 to 8 carbon atoms, cyclohexylene, phenylene, naphthylene, or alkylene of 4 to 12 carbon atoms interrupted by oxygen, with the proviso that two nitrogen atoms never join same carbon atom, a is 1 or 2, - b is 0, 1, or 2, and if a is 1, Rj8 is hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen, -phenyl, benzyl, alkenyl of 3 to 12 carbon atoms, or (R17) 3- and if a is 2, (, 6) b RI8 is -Si- Also of interest are salts derived from: i) a compound of formula I ", and ii) an amine of formula II, -io iii) zirconium, bismuth, or calcium, wherein: R"? is alkyl of 8 to 14 carbon atoms, or alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; R2 is hydrogen, R3 is hydrogen, R "4 is hydrogen or hydroxyl, R" 5 is alkyl of 8 to 14 carbon atoms or O II-CH-P-OH, R-4 m is O, Ri4 and Ri5 'independently of each other, are hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or R14 and R15, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and R18 is alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or is phenyl. The novel amine salts are of good solubility in water (> 1 gram / liter at 25 ° C), and the novel zirconium, bismuth, and calcium salts are poorly soluble in water (< < < 1 gram / liter at 25 ° C). The salts are conveniently prepared by the reaction of a compound of the formula I 'or I "with an amine of the formula II, or, respectively, with a zirconium, bismuth or calcium compound. compound of formula I 'or I "and the amines of formula II with one another, on a temperature scale of 10 ° C to 80 ° C, in particular from room temperature to 60 ° C, as they are, or in a dipolar protic solvent, for example, dichloromethane, or in a protic solvent, for example ethanol, and are reacted. Where the compound of the formula I 'or I "possesses two or more acidic groups in the molecule, then one equivalent of the amine of the formula II is used per individual acid group Some of the compounds of the formula I, I ', or I' are known in the literature, - otherwise, they can be prepared in analogy with British Patent Number GB-A-2, 121, 419; K. Moedritzer et al., J. Org. Chem. 31, 1603-1607 (1966), -Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry] volume XII / 1, pages 483-489 (1963); or volume E2, 302-304 (1982). Some of the amine oxides of the compounds of the formula I, I ', or I ", where m is 1, are known and can be prepared in a known manner, for example by oxidation of the corresponding tertiary amines with a Suitable oxidation agent, such as a peroxide compound, for example hydrogen peroxide, sodium peroxide, percarbonates, perborates, persulfates, peracids The oxidation process is usually carried out in an aqueous medium [see, for example, Hoh et al. , "Hydrogen Peroxide Oxidation of Tertiary Amines", The Journal of the American Oil Chemists' Society, volume LV, No. 7, pages 268-271 (July 1963).] The zirconium, bismuth, and calcium salts of the compounds of the formula I 'or I "can be prepared in a manner known per se. Preferably, a compound of the formula I 'or I "is reacted with a zirconium, bismuth or calcium compound, and the reaction of an alkali metal salt, especially a sodium salt, of the the formula I 'or I "with a compound of zirconium, bismuth, or calcium. As the zirconium, bismuth, or calcium compound, it is convenient to use an organic compound of zirconium, bismuth, or calcium, or an inorganic compound of zirconium, bismuth, or calcium. Examples of the organic zirconium, bismuth, or calcium compounds are, in particular, alcoholates, for example zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, bismuth n-propoxide, bismuth isopropoxide, or carboxylates. , for example acetates, especially zirconium acetate. Examples of the inorganic zirconium, bismuth, or calcium compounds are halides, especially chlorides, nitrates, carbonates, hydroxides, and sulfates. Particularly suitable are zirconium carbonate, zirconium sulfate, zirconium oxide chloride, zirconium hydroxide, bismuth carbonate, bismuth sulfate, bismuth hydroxide, and calcium carbonate. The zirconium and bismuth salts of the compounds of the formula I 'or I "can also be referred to as zirconium and bismuth complexes In the preparation of the zirconium, bismuth, or calcium salts, starting from the compounds of the formula I 'or I "and inorganic zirconium, bismuth, or calcium compounds, such, for example, zirconium carbonate, the reaction is preferably carried out in water at an elevated temperature, in particular at temperatures of 50 ° C to 100 ° C. The reaction also takes place in a mixture of organic solvent with water. Particularly preferred mixtures are those of water with aromatic hydrocarbons, such as toluene or xylene, for example, or alcohols, for example methanol, ethanol, normal propanol, isopropanol, normal butanol, or 2-butanol. A particular preference is given to toluene, ethanol, and 2-butanol. The ratio of the water to the organic solvent can be varied as desired. Preference is given to a ratio of the solvent, for example, of water to toluene, or of water to alcohol (volume: volume) of 1:10 to 10: 1, in particular of 1: 5 to 5: 1, for example 1 : 2 to 2: 1. When using zirconium or bismuth organic compounds such as, for example, zirconium n-propoxide, it is preferred to operate in an anhydrous organic solvent. Suitable organic solvents are all those that are chemically inert to the bases under the conditions of the reaction. Preference is given to aromatic hydrocarbons, such as, for example, toluene or xylene; to aliphatic hydrocarbons such as, for example, pentane, hexane, heptane or octane and their isomeric mixtures, - to halogenated hydrocarbons such as, for example, di- or tri-fluoromethane or 1,2-dichloroethane, - to ethers such such as, for example, diethyl ether, dibutyl ether, 1,4-dioxane, or tetrahydrofuran; and to acetonitrile, dimethyl formamide, dimethyl sulfoxide, or N-methyl pyrrolidone. In the preparation of zirconium or bismuth salts, starting from compounds of the formula I 'or I "and organic zirconium or bismuth compounds, the reaction is preferably carried out in toluene at an elevated temperature, in particular at temperatures of 30 ° C to 80 ° C. The hydrolysis of the zirconium and bismuth complexes of the compounds of the formula I 'or I ", prepared from organic zirconium and bismuth compounds and the compounds of the formula I' or I" it is conveniently carried out as a suspension in water.The products are preferably isolated by filtration of the reaction mixture, and then the residue is dried at room temperature under a high vacuum.The reaction of alkali metal salts of the compounds of the formula I 'or I ", especially the sodium salts, with inorganic zirconium, bismuth, or calcium compounds, for example zirconium sulfate, to give the zirconium, bismuth, or calcium salts of the compounds of the formula to I 'or I ", preferably it is carried out in a solvent, for example, water, or in a mixture of water and an organic solvent at room temperature. The products are preferably isolated by filtration of the reaction mixture, and then the residue is dried at room temperature under a high vacuum. The alkali metal salts of the compounds of the formula I 'or I "can also be prepared on the site, from the corresponding compound of the formula I' or I", with one equivalent of a diluted solution of metal hydroxide alkaline. With respect to the zirconium or bismuth compound employed, the compounds of the formula I 'or I "can be used in excess, in equimolar amounts, or in deficient amounts.The molar ratio of the compound of the formula I' or I" to the compound of zirconium or bismuth can be from 20: 1 to 1:10. Preference is given to a ratio of 10: 1 to 1: 3. Accordingly, the present invention also relates to a process for the preparation of the novel zirconium and bismuth salts, wherein the molar ratio of the compound of the formula I 'or I "to the zirconium or bismuth compound is 20: 1 The present invention further relates to a coating composition comprising: a) an organic binder formed from a film, and b) as a corrosion inhibitor, at least one zirconium or bismuth complex, which can be obtained by reaction of a compound of the formula I 'or I ", or an alkali metal salt thereof, with a zirconium or bismuth compound, wherein the molar ratio of the compound of the formula I' or I" to the zirconium compound or bismuth is from 20: 1 to 1:10, in particular from 10: 1 to 1: 5, for example from 5: 1 to 1: 3. The novel salts of the compounds of the formula I 'or I "can also be complex with free acid (formula I1 or I "), with water, or with other anions, t ales such as hydroxides, which are present in the reaction medium. In the case of zirconium acetates or zirconium alkoxides, acetate anions or alkoxide anions may be present in the zirconium complexes of the compounds of the formula I 'or I. "Based on the comments made above , the percentage of metal content by weight in the zirconium or bismuth complexes of the compounds of formula I1 or I "may be different. Preferred complexes have a metal content of 5 to 50 percent by weight, preferably 5 to 45 percent by weight, for example 5 to 40 percent by weight. The structures of the zirconium and bismuth salts of the compounds of the formula I 'or I "they may vary depending on the method of preparation and the molar proportions of the compounds of the formula I 'or I "and the zirconium or bismuth compounds that are used.Therefore, the present invention also relates to obtainable products. by reacting a compound of the formula I 'or I ", or an alkali metal salt thereof, with a zirconium or bismuth compound. The following examples illustrate the invention in greater detail. The parts and percentages are by weight. ta-jam io 1; Salt with two equivalents of N-ethyl morpholine, of n-octadecylaminobismethylene phosphonic acid. 5.49 grams (0.012 moles) of n-octadecylaminobismethylenephosphonic acid are mixed at room temperature with 2.85 grams (0.024 moles) of N-ethyl morpholine. This gives 8.17 grams (98 percent) of the n-ethyl morpholine salt dibasic of n-octadecylaminobismethylenephosphonic acid as a white powder. Analysis found: C 56.1 percent, - H 10.4 percent, - N 5.9 percent. Calculated analysis: C 55.9 percent, - H 10.4 percent; N 6.1 percent.

Eienrolo 2; Salt with two equivalents of N-ethyl morpholine, of dihexylamine methylene phosphonic acid. Following the procedure of Example 1, 3.35 grams (0.012 moles) of dihexylamine-methyl-phosphonic acid and 2.85 grams (0.024 moles of N-ethyl morpholine give 5.92 grams (96 percent) of the N-ethyl morpholine salt dibasic dihexylamine-methyl-phosphonic acid as a chestnut powder.

Eienrolo 3; Salt with two equivalents of N-ethyl morpholine, of dioctylaminomethylenephosphonic acid. Following the procedure of Example 1, 5.03 grams (0.015 moles) of dioctylaminomethylenephosphonic acid and 3.56 grams (0.03 moles) of N-ethyl morpholine give 8.43 grams (98 percent) of the N-ethyl morpholine salt dibasic dioctylaminomethylene phosphonic acid as a chestnut powder. Analysis found: C 58.7 percent; H 10.9 percent, - N 6.6 percent. Analysis found: C 58.6 percent, - H 11.4 percent; N 7.4 percent. tea? < -nrpi > ? Salt with two equivalents of N-ethyl morpholine, of 2-ethylhexylaminobismethylenephosphonic acid. Following the procedure of Example 1, 5.08 grams (0.016 moles) of 2-ethylhexylaminobismethylenephosphonic acid and 3.8 grams (0.032 moles) of N-ethyl morpholine give 8.77 grams (99 percent) of the morpholine salt N-ethyl dibasic acid 2-ethylhexylaminobismethylenephosphonic acid as a white powder. Analysis found: C 46.2 percent, H 9.1 percent, - N 7.2 percent. Calculated analysis: C 46.3 percent, - H 9.4 percent, -N 7.7 percent.

Example 5; Salt with two equivalents of N-ethyl morpholine, of n-hexadecylaminobismethylene phosphonic acid. Following the procedure of Example 1, 5.15 grams (0.012 moles) of n-hexadecylaminobismethylenephosphonic acid and 2.85 grams (0.024 moles) of N-ethyl morpholine give 7.93 grams (99 percent) of the N-ethyl morpholine salt dibasic acid n-hexadecylaminobismethylene phosphonic acid as a white powder. Analysis found: C 54.5 percent, H 10.3 percent; N 6.0 percent. Calculated analysis: C 54.6 percent; H 10.2 percent; N 6.4 percent.

R-j «am io 6; Salt with two equivalents of N-ethyl morpholine, of n-tetradecylaminobismethylene phosphonic acid. Following the procedure of Example 1, 6.02 grams (0.015 moles) of n-tetradecylaminobismethylenephosphonic acid, and 3. 56 grams (0.03 moles) of N-ethyl morpholine, give 9.4 grams (98 percent) of the N-ethyl morpholine salt dibasic of n-tetradecylaminobismethylenephosphonic acid as a white powder. Analysis found: C 53.2 percent; H 10.2 percent; N 6.3 percent, -. Calculated analysis: C 53.2 percent, - H 10.1 percent; N 6.7 percent. ? e-jo pí 7; Salt with two equivalents of N-ethyl morpholine, of n-dodecylaminobismethylene phosphonic acid. Following the procedure of Example 1, 10 grams (0.027 moles) of n-dodecylaminobismethylenephosphonic acid and 6.36 grams (0.054 moles) of N-ethyl morpholine give 16.2 grams (99 percent) of the N-ethyl morpholine salt dibasic acid n-ethyl -dodecylaminobismethylene phosphonic acid as a white powder. Analysis found: C 52.2 percent; H 10.1 percent, - N 6.7 percent, -. Calculated analysis: C 51.7 percent; H 9.8 percent; N 7.0 percent.

Example 8: Salt with two equivalents of N-ethyl morpholine, of n-deci aminobismethylene phosphonic acid. Following the procedure of Example 1, 5.18 grams (0.015 mole) of n-decylaminobismethylene phosphonic acid and 3.56 grams (0.03 mole) of N-ethyl morpholine give 8.67 grams (99 percent) of the n-ethyl morpholine salt dibasic of n-decylaminobismethylene phosphonic acid as a white powder. Analysis found: C 47.6 percent; H 9.3 percent; N 6.8 percent, -. Calculated analysis: C 50.1 percent, - H 9.6 percent; N 7.3 percent.

Example 9; Salt with two equivalents of N-ethyl morpholine, of n-octylaminobismethylene phosphonic acid. Following the procedure of Example 1, 3.81 grams (0.012 moles) of n-octylaminobismethylenephosphonic acid and 2.85 grams (0.024 moles) of N-ethyl morpholine give 6.51 grams (98 percent) of the morpholine salt N-ethyl dibasic acid n-octylaminobismethylene phosphonic acid as a white powder.

Example 10; Salt with two equivalents of N-ethyl morpholine, of n-hexylaminobismethylenephosphonic acid. Following the procedure of Example 1, 2.89 grams (0.01 moles) of n-hexylaminobismethylenephosphonic acid and 2.38 grams (0.02 moles) of N-ethyl morpholine, give 5.24 grams (99 percent) of the N-ethyl morpholine salt dibasic of n-hexylaminobismethylenephosphonic acid as a white powder.

Example 11; Salt with an equivalent of N, N-dimethyl aniline, of n-dodecylaminobismethylene phosphonic acid. To a suspension of 4.85 grams (0.013 moles) of n-dodecylaminobismethylenephosphonic acid in 35 milliliters of dichloromethane, 1.58 grams (0.013 moles) of N, N-dimethyl aniline are added, - the mixture is stirred at room temperature for 1 hour , and then the dichloromethane is distilled over a rotary evaporator, to give 6.46 the n-dodecylaminobismethylene phosphonic acid N, N-dimethyl monobasic aniline salt as a white powder. Analysis found: C 51.8 percent, - H 8.9 percent; N 5.3 percent, -. Calculated analysis: C 53.4 percent; H 9.0 percent, - N 5.7 percent.

Example 12; Salt with an N-ethyl morpholine equivalent of n-dodecylaminobismethylene phosphonic acid. Following the procedure of Example 11, 4.85 grams (0.013 moles) of n-dodecylaminobismethylenephosphonic acid and 1.54 grams (0.013 moles) of N-ethyl morpholine give 6.41 grams of the N-ethyl morpholine salt monobasic of n-dodecylaminobismethylene phosphonic acid as a powder White. Analysis found: C 47.8 percent; H 9.7 percent, - N 5.5 percent, -. Calculated analysis: C 49.2 percent, - H 9.5 percent, - N 5.7 percent. ig «a pio 13; Salt with three equivalents of N-ethyl morpholine, of n-dodecylaminobismethylene phosphonic acid. Following the procedure of Example 11, 7.46 grams (0.02 moles) of n-dodecylaminobismethylenephosphonic acid and 6.91 grams (0.06 moles) of N-ethyl morpholine give 15.27 grams of the basic N-ethyl morpholine salt of n-dodecylaminobismethylene phosphonic acid as a beige resin.

Example 14; Salt with an equivalent of trietanolic amine, of n-dodecylaminobismethylene phosphonic acid. Following the procedure of Example 11, 4.85 grams (0.013 moles) of n-dodecylaminobismethylenephosphonic acid and 1.94 grams (0.013 moles) of trietanolic amine give 6.87 grams of monobasic trietanolic amine salt of n-dodecylaminobis-methylene phosphonic acid as a white powder. Analysis found: C 45.7 percent; H 9.5 percent; N 5.5 percent, -. Calculated analysis: C 46.0 percent; H 9.3 percent; N 5.4 percent. g-j «a pio 15; Salt with an equivalent of triethyl amine, of n-dodecylaminobismethylene phosphonic acid. Following the procedure of Example 11, 4.85 grams (0.013 moles) of n-dodecylaminobismethylenephosphonic acid and 1.32 grams (0.013 moles) of trityl amine give 6.26 grams of monobasic triethyl amine salt of n-dodecylaminobismethylene phosphonic acid as a white powder. Analysis found: C 49.5 percent; H 10.5 percent; N 5.6 percent, -. Calculated analysis: C 50.6 percent; H 10.2 percent, - N 5.9 percent. g «ampi ifii Salt with two equivalents of trietanolic amine, of n-dodecylaminobismethylene-phosphonic acid. Following the procedure of Example 11, 4.85 grams (0.013 moles) of n-dodecylaminobismethylenephosphonic acid and 3.88 grams (0.026 moles) of trietanolic amine give 8.89 grams of the dibasic trietanolic amine salt of n-dodecylaminobismethylene phosphonic acid as a white powder . Analysis found: C 45.0 percent; H 10.1 percent, - N 6.0 percent, -. Calculated analysis: C 46.5 percent; H 9.5 percent, - N 6.3 percent.

Example 17; Salt with two equivalents of trietanolic amine, of n-decylaminobismethylene phosphonic acid. Following the procedure of Example 11, 2.41 grams (0.007 moles) of n-decylaminobismethylenephosphonic acid and 2.08 grams (0.014 moles) of trietanolic amine give 3.5 grams (78 percent) of the dibasic trietanolic amine salt of n-decylaminobismethylene phosphonic acid as a white powder. Analysis found: C 43.7 percent; H 9.1 percent, - N 6.1 percent, -. Calculated analysis: C 44.8 percent, - H 9.2 percent; N 6.5 percent.

Example 18; Salt with two equivalents of trietanolic amine, of n-octylaminobismethylenephosphonic acid. Following the procedure of Example 11, 2.22 grams (0.007 moles) of n-octylaminobismethylenephosphonic acid and 2.08 grams (0.014 moles) of trietanolic amine give 3.3 grams (77 percent) of the dibasic trietanolic amine salt of n-octylaminobismethylenephosphonic acid as a white powder. Analysis found: C 42.4 percent, - H 8.9 percent; N 6.4 percent, -. Calculated analysis: C 42.9 percent, - H 9.0 percent; N 6.8 percent.

Example 19; Salt with two equivalents of trietanolic amine, of n-hexylaminobismethylenephosphonic acid. Following the procedure of Example 11, 2.89 grams (0.01 mole) of n-hexylaminobismethylene phosphonic acid and 2.98 grams (0.02 mole) of trietanolic amine, give 3.5 grams (60 percent) of the dibasic trietanolic amine salt of n-hexylaminobismethylenephosphonic acid as a white resin. Analysis found: C 40.5 percent, - H 8.8 percent; N 7.1 percent, -. Calculated analysis: C 40.9 percent; H 8.8 percent; N 7.2 percent. g «ampio 20; Salt with two equivalents of N-ethyl morpholine, of n-dodecylaminobismethylenephosphonous acid. a) 16.2 grams (0.2 mole) of an aqueous solution of formaldehyde (37 percent) receive added portions, first 18.54 grams (0.1 moles) of n-dodecyl amine, and then 26.4 grams (0.2 moles) of hypophosphorous acid (solution watery to 50 percent). Then the mixture is stirred at 25 ° C for 1 hour. After filtration and drying of the filter residue in a vacuum oven at 50 ° C, 19.34 grams (54 percent) of n-dodecylaminobismethylene phosphonous acid is obtained as a beige solid. Calculated analysis: C 49.3 percent; H 9.7 percent; N 4.1 percent, -. Analysis found: C 47.4 percent; H 9.9 percent, - N 4.0 percent. b) 3.41 grams (0.01 mole) of n-dodecylaminobismethylenephosphonous acid as Example 20a, are mixed at room temperature with 2.3 grams (0.02 mole) of N-ethyl morpholine. This gives the N-ethyl morpholine salt dibasic of n-dodecylaminobismethylene phosphonous acid. Calculated analysis: C 54.6 percent; H 10.4 percent, - N 7.4 percent, -. Analysis found: C 52.9 percent; H 10.9 percent; N 7.1 percent. gj «pin 21- Zirconium complex, of n-dodecylaminobis-methylene phosphonic acid. A suspension of 18.67 grams (0.05 moles) of n-dodecylaminobismethylenephosphonic acid and 14.14 grams (0.05 moles) of basic zirconium carbonate (zirconium content: 32.25 percent) in a mixture of 200 milliliters of water and 20 milliliters of ethanol, heat at 90 ° C with stirring, and keep at this temperature for 1 hour. After cooling to 25 ° C, it is filtered, and the filter residue is dried in a vacuum oven at 50 ° C, to give 25.9 grams of the zirconium complex of n-dodecylaminobismethylene phosphonic acid as a white powder. Analysis found: C 31.4 percent, - H 6.8 percent; N 2.3 percent Zr 31.3 percent.

Example 22; Calcium salt, of n-dodecyl aminobismethylene phosphonic acid. A suspension of 3.73 grams (0.01 moles) of n-dodecylaminobismethylenephosphonic acid and 1.0 grams (0.01 moles) of calcium carbonate in 15 milliliters of water is heated to 90 ° C and maintained at this temperature for 2.4 hours. After cooling to 25 ° C, it is filtered, and the filter residue is dried using a vacuum pump. This gives 4.09 grams (99 percent) of the calcium salt of n-dodecylaminobismethylenephosphonic acid as a white powder. Calculated analysis: C 40.9 percent; H 7.6 percent; N 3.4 percent, -. Analysis found: C 41.0 percent; H 7.6 percent; N 3.3 percent. g-j «to io 23; 5-hydroxypentinylaminobismethylenephosphonic acid. To a solution of 36.1 grams (0.35 moles) of 5-aminopentanol in 25 milliliters of water are added, with ice-cooling, stirring, and in succession, 82.8 grams (0.84 moles) of hydrochloric acid (37 percent in water). ) and a solution of 57.4 grams (0.7 moles) of phosphorous acid in 45 milliliters of water. Following the addition of 120.1 grams (1.4 moles) of formaldehyde (35 percent in water), the mixture is heated to 85 ° C, and kept at this temperature for 3 hours. To isolate the product, the oil obtained immediately after concentration on a rotary evaporator is recrystallized while still hot, from an ethanol / water mixture. For purification, the resulting white powder is recrystallized three times while still hot, from a methanol / water mixture, to give 35.3 grams (34.6 percent) of 5-hydroxypentinylaminobismethylenephosphonic acid as a white powder. Analysis calculated for: C7H19NP207 C 28.9 percent; H 6.6 percent, - N 4.8 percent, -. Analysis found: C 28.9 percent; H 6.7 percent; N 4.6 percent.

Example 24; Salt with two equivalents of N-ethyl morpholine, of 12- [bis (phosphonomethyl) amino] dodecanoic acid. 4.43 grams (0.011 moles) of 12- [bis (phosphonomethyl) amino] dodecanoic acid are mixed with 2.53 grams (0.022 moles) of N-ethyl morpholine. This gives the salt of 12- [bis (phosphonomethyl) -amino] dodecanoic acid with two equivalents of N-ethyl morpholine as a beige powder. Analysis calculated for: C ^ H ^ jOj ^: C 49.3 percent; H 9.1 percent, - N 6.6 percent, -. Analysis found: C 47.5 percent, - H 8.9 percent, - N 6.1 percent. gÍ * > tnP1 > 9t Testing the salts in a coating formulation. In order to prepare the coating formulation (acrylic dispersion based on Maincote HG-54), components 1 to 8 (formulation without salt of amine) and components 1 to 9 (formulation comprising an amine salt) are used in the mentioned sequence (see Table 1). a) Methylcarbitol R: diethylene glycol monomethyl ether (Union Carbide), - b) Orotan® 165: dispersion aid (Rohm and Haas Company); c) Triton® CF 10: non-ionic wetting agent (Rohm and Haas Comp.), - d) Drew Plus® TS 4380: antifoam (Drew Chem. Corp.), - e) Acrysol® RM 8: non-ionic thickener (Rohm and Haas Comp. .); f) Bayferrox® 130 M: red iron oxide (Bayer AG), - g) Millicarb®: calcium carbonate (Omya), - h) Maincote® HG-54: acrylic dispersion (Rohm and Haas Comp.); i) TexanolR: Coalescent (Eastman Chem. Prod., Inc.); k) dibutyl phthalate: plasticizer (Eastman Chem. Prod., Inc.); 1) sodium nitrite: evaporation corrosion inhibitor (Fluka), - m) Drew1 T 4310: nonionic antifoam (Drew Chem. Corp.).

Components I to 8 or 1 to 9 are dispersed using a high speed agitator at 3,000 revolutions per minute to a milled finite grade or to a milled particle nature of < 15 mins. The result of the dispersion of the pigment paste thus obtained is evaluated by determining the value of the milling measure (ISO 1524). The amount of the novel salts employed is based on the total solids content of the salt-free formulation (total solids content: 47 percent). According to the above, an addition of, say, 1.0 percent amine salt to 100 grams of dispersion, denotes, for example, an amount of 0.47 grams. To finish the coating formulation, components 10 to 16 of Table 1 are added at a reduced agitation speed (1000 revolutions per minute) in the mentioned sequence. Subsequently, the pH of the formulation is verified, and if appropriate, it is adjusted before being applied, to a value of 8 to 8.5, using an ammonia solution (concentration of 25 percent). The coating formulation can be applied in undiluted form by airless, spread, or roller spraying, or, after dilution, by conventional spraying. The dilution to the desired spray viscosity is achieved by the addition of butyl glycol / water (1: 1 w / w). The coating formulations are applied to steel panels (19 x 10.5 centimeters) of the Bonder type (degreased steel cold rolled; manufactured by Chemetall, Frankfurt am Main / Germany) in a coating thickness that, after drying, adds up to 50-55 microns. Drying conditions: 10 days at room temperature. Before starting weathering, the "coating films" suffer a defined damage in the form of a parallel cut (ie, parallel to the edge of the longest panel) using a Bonder cross-cut instrument (model 205) manufactured and sold by Lau, 5870 Hemer / Germany). The edges of the panel are protected by the application of a shore protector (Icosit® 255, manufactured by Inertol AG, Winterthur / Switzerland). Subsequently the samples are subjected to accelerated weathering in a salt spray test in accordance with DIN 50 021 SS for 168 hours (Table 2), or to a humidity test according to ASTM D 4585-87 for 330 hours (Table 3) . The evaluation of the results is based on the relevant DIN standards according to an evaluation key, by the indication of a corrosion protection value FPC (Corrosion Protection Factor). The FPC is an additive term composed of an evaluation of the coating (film) and an evaluation of the visible corrosion under the film, and of the appearance of the metal surface, and has a maximum of 12 points. The maximum individual values are 6 points each. The higher the FPC, the better the protection against corrosion. As an additional evaluation criterion, "migration under the film in the wet state" (cathodic delamination) along the side with the artificial damage is determined, after the end of the salt spray test, in accordance with DIN 53 167. The lower the desiamination, the more effective the proven corrosion inhibitor will be. After the end of the humidity test, the wet adhesion of the coating formulation according to DIN 53 151 is determined, making a cross cut followed by the tape tear test. According to DIN 53 151 (scale from Gt 0 to Gt 5), a cross value of Gt 0 corresponds to a completely intact adhesion of the coating film, while Gt 5 corresponds to an inadequate adhesion. Table 2: Salt spray test, 168 hours, coating thickness from 50 to 55 microns Table 3; Moisture test, 330 hours, coating thickness from 45 to 50 microns

Claims

NOVELTY OF THE INVENTION Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS 1. A coating composition, which comprises: a) an organic film-forming binder, and b) as a corrosion inhibitor, cu) at least one compound of the formula I: R.-N C P-OH (I) I I I R5 R3 R4 wherein: Rj is alkyl of 4 to 12 carbon atoms substituted by hydroxyl, carboxyl, or amino; or R, and R5, together with the nitrogen atom to which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which I'm interrupted \ do for oxygen, sulfur, or N-R6 > R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, - or are benzyl, R4 it's hydroxyl, OR R5 is -CH-P-OH, OH R6 is alkyl of 1 to 18 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, and m is 0 or 1; or ß) at least one salt derived from: i) a compound of the formula I ': wherein: R 'is hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 3 to 25 carbon atoms interrupted by oxygen, sulfur, or /. N- R7 »'alkyl of 2 to 25 carbon atoms substituted by hydroxyl, carboxyl, or amino; alkenyl of 2 to 24 carbon atoms, cycloalkyl of 4 to 15 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl from 7 to 9 carbon atoms, or or R'a and R'5 together with the nitrogen atom to which they are attached, form a 5-, 6-, or 7-membered heterocyclic ring, which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, or that is interrupted by oxygen, sulfur, \ N-Re R'4 is hydrogen, hydroxyl, or -0R8, R'5 is hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 3 to 25 carbon atoms interrupted by oxygen, \ sulfur, or .N-R7 • 'alkenyl of 2 to 24 atoms of carbon, cycloalkyl of 4 to 15 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl of 7 to 9 carbon atoms, or O -CH2- • PP-OH I R 'R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R8 is alkyl of 1 to 6 carbon atoms, cycloalkyl of 4 to 15 carbon atoms, or phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, - and with the proviso that, if R ', or R' 5 is hydrogen, let 0, - and ii) an amine of formula II wherein: R14 and R) 5, independently of one another, are hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 2 to 24 carbon atoms. carbon substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur, - phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, - alkenyl of 3 to 24 carbon atoms or or R14 and R15, together with the nitrogen atoms with which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or which is substituted by alkyl of the 4 carbon atoms, or that is interrupted by oxygen, sulfur, \ I N-R7 / R16 is alkyl of 1 to 25 carbon atoms, alkyl of 2 to 25 carbon atoms which is interrupted by oxygen or sulfur; hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkenyl of 2 to 24 carbon atoms, R17 is hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkoxy of 2 to 18 carbon atoms which is interrupted by oxygen or sulfur , - and if b is 0, three radicals R [7 are together N (CH2CH20-) • ,, X is a direct bond, alkylene of 1 to 18 carbon atoms, alkylidene of 2 to 20 carbon atoms, phenylalkylidene of 7 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, phenylene or unsubstituted naphthylene or substituted by alkyl from 1 to 4 carbon atoms; or is alkylene of 4 to 18 carbon atoms which is interrupted by oxygen, sulfur, or with the proviso that two nitrogen atoms never join the same carbon atoms, a is 1 or 2, b is 0, 1, or 2, and if a is 1, R18 is hydrogen, alkyl of 1 to 25 carbon atoms. carbon, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms which is interrupted by oxygen or sulfur; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, - alkenyl of 3 to 24 atoms carbon if a is 2, -18 is and with the condition that, if in the compound of the formula I ', R', is alkyl of 1 to 12 carbon atoms, -CH-P-OH OH O or 2-hydroxyethyl, R's is II 5 -CH2-P-OH, 2 I OH R2 and R3 are hydrogen, R'4 is hydroxyl, and m is 0, and if in the compound of the formula II a is 1 and X is a direct bond, then at least one of the radicals R, 4, R (5, and R18 is different from hydrogen, - or iii) zirconium, bismuth, or calcium. 2. A coating composition according to claim 1, wherein R2 and R3 are hydrogen. 3. A coating composition according to claim 1, wherein R is alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl. 4. A coating composition according to claim 1, wherein: R'j is alkyl of 5 to 18 carbon atoms, or alkyl of 5 to 12 carbon atoms substituted by hydroxyl or carboxyl; R'4 is hydrogen or hydroxyl, and R'5 is alkyl of 5 to 25 carbon atoms, or -CH2- OH.
2 A coating composition according to claim 1, wherein: Ri4 and Ri5 independent of one another, are hydrogen, alkyl of 1 to 8 carbon atoms, or alkyl of 2 to 14 carbon atoms substituted by hydroxyl; or R14 and Ri5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and R18 is alkyl of 1 to 14 carbon atoms, alkyl of 2 to 14 carbon atoms substituted by hydroxyl; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; or it is benzyl. 6. A coating composition according to claim 1, wherein: Rj is alkyl of 5 to 12 carbon atoms substituted by hydroxyl, carboxyl, or amino, - or R, and R5, together with the nitrogen atom with the which are joined, form a heterocyclic ring of 5, 6, or 7 members that is interrupted by oxygen, sulfur \ N-Rfi R'j is alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms which is interrupted by oxygen, sulfur, or N-R,; alkyl of 5 to 20 carbon atoms / substituted by hydroxyl, carboxyl, or amino; alkenyl of 5 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms R, O carbon; benzyl or -C P-OH or R1 | and R'5, together I I R3 R'4 with the nitrogen atom to which they are attached, they form a 6-membered heterocyclic ring, which is unsubstituted or is substituted by alkyl of 1 to 4 carbon atoms or is \ interrupted by oxygen, sulfur, or N-R / R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl; R4 is hydroxyl, R'4 is hydrogen, hydroxyl, or -OR8, O R5 is --CH - P-OH, 2 I OH R'5 is hydrogen, alkyl of 5 to 20 carbon atoms. alkyl of 5 to 20 carbon atoms that is interrupted by \ oxygen, sulfur, or N-R7. alkenyl from 5 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms O carbon; benzyl, or rH L 0H R6 is alkyl of 1 to 12 carbon atoms or benzyl, m is 0 or 1, R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R8 is alkyl of 1 to 6 carbon atoms, cyclohexyl, or phenyl, R14 and R15, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms substituted by hydroxyl, alkyl of 3 to 20 carbon atoms interrupted by oxygen or sulfur, - phenylalkyl of 7 to 9 carbon atoms, - alkenyl of 3 to 20 carbon atoms, or or R14 and Rj5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring, which is interrupted by oxygen, sulfur, or N-R • / 7 ' R16 is alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 20 carbon atoms, Ri7 is hydroxyl , alkoxy of 1 to 12 carbon atoms, or alkoxy of 2 to 12 carbon atoms interrupted by oxygen or sulfur; and b is 0, three radicals RJ7 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, phenylalkylidene of 7 to 12 carbon atoms , cyclohexylene of 5 to 8 carbon atoms, phenylene, naphthylene, or alkylene of 4 to 18 carbon atoms interrupted by oxygen or sulfur, with the proviso that two nitrogen atoms never join the same carbon atom. a is 1 or 2, b is 0, 1, or 2, and if a is 1, R18 is hydrogen, alkyl of 1 to 20 carbon atoms, alkyl of 2 to 20 carbon atoms substituted by hydroxyl, alkyl of 3 to 20 carbon atoms interrupted by oxygen or sulfur; phenyl, phenylalkyl of 7 to 9 carbon atoms, alkenyl of 3 to 20 carbon atoms, / N \ if a is 2, 7. A coating composition according to claim 1, wherein: R is alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; or R and R5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur. R'j is alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms interrupted by oxygen or sulfur, -alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; alkenyl of 5 to 10 carbon atoms, cyclohexyl, phenyl, or benzyl, or R'j and R'5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur. R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, or benzyl, R4 is hydroxyl, R'4 is hydrogen or hydroxyl, OR R5 is __CH p_OH f 2 I OH R'5 is alkyl of 5 to 20 carbon atoms, alkyl of 5 to 20 carbon atoms interrupted by oxygen or sulfur; alkenyl of 5 to 20 carbon atoms, cyclohexyl, phenyl, benzyl, or _CH P -OH R'_ m is 0, Rj4 and 15, independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen or sulfur , - benzyl, alkenyl of 3 to 12 carbon atoms, or -x-s (R17) 3-b or RI4 and R15, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - RI6 is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms interrupted by oxygen or sulfur; hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms, R17 is hydroxyl or alkoxy of 1 to 12 carbon atoms; and if b is 0, three radicals R17 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 8 carbon atoms, cyclohexylene, phenylene, naphthylene, or is alkylene of 4 to 12 carbon atoms interrupted by oxygen, with the proviso that two nitrogen atoms never join the same carbon atom, a is 1 or 2, b is 0, 1, or 2, and if a is 1, R18 is hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen; phenyl, benzyl, alkenyl of 3 to 12 carbon atoms or if a is 2, (R,? R18 is -si- • I (R1) 2-b 8. A coating composition according to claim 1, wherein - Rj is alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl, R ', is alkyl of 5 to 18 carbon atoms, or alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl; R2 is hydrogen, R3 is hydrogen, R4 is hydroxyl, R'4 is hydrogen or hydroxyl, O II R5 is -CH, -P-OH, 2 I OH R'5 is alkyl of 5 to 18 carbon atoms O II -CH-P-OH, m is 0, Ri4 and Ri5"independently of each other, are hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or R14 and R15, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and R18 is alkyl of 1 to 4 carbon atoms, alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or is phenyl. 9. A coating composition according to claim 1, wherein the coating composition is a coating material. 10. A coating composition according to claim 1, wherein the coating composition is an aqueous coating material. 11. A coating composition according to claim 1, wherein the component (a) is an epoxy resin, a polyurethane resin, an amine resin, an acrylic resin, an acrylic copolymer resin, a polyvinyl resin, a phenolic resin, a styrene / butadiene copolymer resin, a vinyl / acrylic copolymer resin, a polyester resin, or an alkyd resin, or a mixture of two or more of these resins, or a basic or acid aqueous dispersion of these resins or mixtures of these resins, or an aqueous emulsion of these resins or mixtures of these resins. 12. A coating composition according to claim 1, which additionally comprises one or more components taken from the class consisting of pigments, colorants, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters. , antioxidants, light stabilizers, and curing catalysts. 13. A coating composition according to claim 1, wherein the component (b) is present in an amount of 0.01 to 20 percent, based on the wt of the total solids content of the coating composition. A process for the preparation of a coating composition comprising a corrosion inhibitor according to claim 1, which comprises mixing an organic film-forming binder with a component (b) according to claim 1. 15. A compound of the formula I: < ? > m R2 OR II R, -N- -P-OH (I) R5 R3 R4 wherein: Rj is alkyl of 4 to 12 carbon atoms substituted by hydroxyl or amino, - or R, and R5, together with the nitrogen atom to which they are attached, is a 5-, 6-, or 7-membered heterocyclic ring , which is unsubstituted or which is substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen,? sulfur, or N-Rfi / R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, - or benzyl, R4 is hydroxyl, R6 is alkyl of 1 to 18 carbon atoms, or phenylalkyl of 7 to 9 carbon atoms, and m is 0 or 1; and with the proviso that the compound of formula III is excluded: (III) 16. A compound according to claim 15, wherein: R is alkyl of 5 to 11 carbon atoms substituted by hydroxyl; or Rj and R5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, or benzyl, R4 is hydroxyl, OR R5 is -CH, -P-OH OH is 0. 17. A compound according to claim 15, wherein: Rj is alkyl of 5 to 8 carbon atoms substituted by hydroxyl, R2 is hydrogen, R3 is hydrogen, R4 is hydroxyl, OR II R5 is -CH_p__OH. And 2 I OH is 0 18. A salt derived from i) a compound of the formula I ": wherein: R "? is alkyl of 8 to 14 carbon atoms, alkyl of 4 to 14 carbon atoms substituted by hydroxyl, carboxyl, or Not me; alkenyl of 8 to 14 carbon atoms, or or R "j and R" 5, together with the nitrogen atom with which they are attached, form a heterocyclic ring of 5, 6, or 7 members, which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms. \ carbon, or that is interrupted by oxygen, sulfur or N-R6; R2 and R3, independently of one another, are hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, - or are benzyl, R "4 is hydrogen or hydroxyl, R" 5 is hydrogen, alkyl of 8 to 14 carbon atoms, alkenyl of 2 to 24 carbon atoms, or -CH p OH R " R6 is alkyl of 1 to 18 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, and is 0 or 1; with the proviso that, if R ", or R" 5 is hydrogen, m is 0; and ii) an amine of formula II: wherein: R | 4 and Rj5, independently of one another, are hydrogen, alkyl of 1 to 25 carbon atoms, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur, - phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, -alkenyl of 3 to 24 carbon atoms or -? g¡ \ (R, 7) 3 * or Rj and R15, together with the nitrogen atoms with which they are attached, form a 5-, 6-, or 7-membered heterocyclic ring, which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, or which is interrupted by oxygen, sulfur, or N-R7; R7 is hydrogen or alkyl of 1 to 6 carbon atoms, R6 is alkyl of 1 to 25 carbon atoms, alkyl of 2 to 25 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 18 carbon atoms. carbon, or alkenyl of 2 to 24 carbon atoms, R17 is hydroxyl, alkoxy of 1 to 18 carbon atoms, or alkoxy of 2 to 18 carbon atoms interrupted by oxygen or sulfur, - and if b is 0, three radicals Rj7 they are together N (CH2CH, 0-) 3, X is a direct bond, alkylene of 1 to 18 carbon atoms, alkylidene of 2 to 20 carbon atoms, phenylalkylidene of 7 to 20 carbon atoms, cycloalkylene of 5 to 8 atoms of carbon, phenylene or naphthylene unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, - or alkylene of 4 to 18 carbon atoms which is interrupted by oxygen, sulfur, or N-R7, with the proviso that they never join two atoms of nitrogen at the same carbon atoms, a is 1 or 2, b is 0, 1, or 2, and if a is 1, R18 is hydrogen, at 1 to 25 carbon atoms, alkyl of 2 to 24 carbon atoms substituted by hydroxyl, alkyl of 3 to 25 carbon atoms interrupted by oxygen or sulfur; phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; phenylalkyl of 7 to 9 carbon atoms which is unsubstituted or which is substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, - alkenyl of 3 to 24 carbon atoms, if a is 2, (R «) R18 is - if -; and with the proviso that (R 17) 2-3 the compound of formula II is not ammonia, trietanolic amine, or ethyl amine, - or iii) zirconium, bismuth, or calcium. 19. A salt according to claim 18, wherein: R "j is alkyl of 8 to 14 carbon atoms, alkyl of 5 to 14 carbon atoms substituted by hydroxyl or carboxyl; or is alkenyl of 8 to 12 carbon atoms, or R "j and R" 5, together with the nitrogen atom with which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, - R2 and R3, independently one of the other, are hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, or benzyl, R "is hydrogen or hydroxyl, R" 5 is alkyl of 8 to 14 carbon atoms, alkenyl OR II of 5 to 20 carbon atoms, or -CH¿-P-OH, R "4 m is 0, R 14 and R 15, independently of one another, are hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms interrupted by oxygen or sulfur; benzyl, alkenyl / (Riß? 3 to 12 carbon atoms, or - X - Si; or RJ4 and R15, (R17) 3- together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen or sulfur, R, 6 is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms interrupted by oxygen or sulfur, -hydroxyl, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms , Rj7 is hydroxy or alkoxy of 1 to 12 carbon atoms, and if b is 0, three radicals Ri7 are together N (CH2CH20-) 3, X is a direct bond, alkylene of 1 to 8 carbon atoms, cyclohexylene, phenylene, naphthylene, or alkylene of 4 to 12 carbon atoms interrupted by oxygen, with the proviso that two nitrogen atoms never join the same carbon atom, a is 1 or 2, - b is 0, 1, or 2 , and if a is 1, R, 8 is hydrogen, alkyl of 1 to 12 carbon atoms, alkyl of 2 to 12 carbon atoms substituted by hydroxyl, alkyl of 3 to 12 carbon atoms, carbon, interrupted by oxygen, -phenyl, benzyl, alkenyl of 3 to 12 carbon atoms, or if a is 2, 20. A salt according to claim 18, wherein: R "j is alkyl of 8 to 14 carbon atoms, or alkyl of 5 to 11 carbon atoms substituted by hydroxyl or carboxyl, R 2 is hydrogen, R 3 is hydrogen, R" 4 is hydrogen or hydroxyl, R "5 is alkyl of 8 to 14 carbon atoms or O II -CH-P-OH, R" 4 m is 0, R14 and R15, independently of one another, are hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or Rj4 and R | 5, together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring interrupted by oxygen, X is a direct bond, a is 1, and R18 is alkyl of 1 to 4 carbon atoms. carbon, or alkyl of 2 to 4 carbon atoms substituted by hydroxyl; or is phenyl. 21. A process for the protection of a corrodable metal substrate, which comprises applying thereto, a coating composition according to claim 1, and then drying and / or curing it. 22. A process for the preparation of a corrosion-resistant surface coating on a corrodable metal surface, which comprises treating this surface with a coating composition according to claim 1, and then drying and / or curing it. 23. A process for pre-treating metal surfaces, which comprises applying an aqueous solution of a component (b) according to claim 1, to the metal surface, and drying it. 24. The use of component (b) defined in claim 1, as a corrosion inhibitor in coating compositions for metal surfaces.