CA1316685C - Corrosion-inhibiting aqueous coating compositions - Google Patents
Corrosion-inhibiting aqueous coating compositionsInfo
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- CA1316685C CA1316685C CA000494944A CA494944A CA1316685C CA 1316685 C CA1316685 C CA 1316685C CA 000494944 A CA000494944 A CA 000494944A CA 494944 A CA494944 A CA 494944A CA 1316685 C CA1316685 C CA 1316685C
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- coating composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Corrosion-inhibiting aqueous coating compositions Abstract of the Disclosure An aqueous corrosion-inhibiting coating composition containing a) an aqueous film-forming binder and b) as the corrosion inhibitor, an effective amount of an aliphatic or cycloaliphatic di-, tri- or tetra-carboxylic acid which is substituted in its aliphatic or cycloaliphatic radical by at least one group of the formula I
I
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, - CN, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino or carbamoyl group, and also base addition salts of these compounds.
I
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, - CN, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino or carbamoyl group, and also base addition salts of these compounds.
Description
- 131 6G~S
Corrosion-inhibiting aqueous coat;ng compositions The present invention relates to aqueous coating compositions which, by virtue of containing certain compounds, are capable of inhibiting the corrosion of metallic sub-strates, especially ferrous metals. The compounds are aliphat;c or cycloaliphatic carboxylic acids containing a heterocyclic radical.
Protection against corrosion is one of the most important duties of organic coating compositions for metal substrates. Many suggestions for improving the protection of coatings against corrosion are to be found in the litera-ture, for example in H. Kittel, Lehrbuch der Lacke und Be-schichtungen ("Textbook of Paints and Coatings"), volume V, Stuttgart l977, 46-103. On the one hand, the barrier function of the coating composition can be improved, in order to keep corrosive agents, such as oxygen, water and ions, away from the metal surface~ On the other hand, it is possible to employ corrosion-inhibiting pigments which intervene chemically or electrochemically in the corrosion process, for example by the formation of insoluble deposits with corrosion products or by passivation (polarisation~ of the metal surface. Metal chromates and lead compounds rank amongst the most effective corrosion-inhibiting pigments. Much use has been made of metal chromates, particularly because they inhibit both anodic and cathodic corrosion. Nowadays there are certain objections to the use of chromates owing to their potential carcinogenic action. Similarly, there are objections to the use of lead compounds owing to their chronic toxicity.
Metal salts of organic compounds have also been frequently suggested as corrosion inhibitors. Thus, for example, European Patent Specification 3,817 recommends the use of zinc or lead salts of hydroxy or mercapto compounds of 5-membered or 6-membered heterocyclic compounds containing the characteristic group ~ 1 3 1 6 6 ~?~
-N=gH or -N=~-Typical examples of these are the Zn or Pb salts of 2-mer-captobenzthiazole.
In a separate patent Application, certain heterocyclic carboxylic acids and salts thereof have been described which can be used as corrosion inhibitors for coating compositions, which makes it possible to formulate highly effective corrosion-inhibiting paints which are free from chromates and lead.
Organic corrosion inhibitors of this type are not pigments, and their use in coating compositions therefore permits a free choice of pigments or extenders. In the fieLd of coating composit;ons, however, here has hitherto been doubt whether the addition of organic corrosion inhibitors on their own makes possible adequate protection, in practice, against corros;on (Farbe und Lack _ ~1981) 787).
The tw;n factors of env;ronment protection and of economy of natural resources are fundamental to any modern chemical manufacture. In the case of surface coatings manufacture, these factors have influenced a trend away from the expensive, hazardous and polluting hydrocarbon solvents towards water-borne coatings.
It has now been found that certain heterocyclic carboxylic ac;ds and their salts are effective corrosion inhibitors in such water-borne coatings.
It is surprising, therefore, that the organic corrosion inhibitors used according to the invention have a corrosion-inhibit;ng effect in aqueous coat;ng compos;tions which is in certain cases equal to that of chromate or lead pigments, or even surpasses the latter.
The present invention relates, therefore, to an aqueous corrosion-inhibiting coating composition containing a) an aqueous film-form;ng b;nder and .. . .
1 3 1 66~5 b) as the corrosion inhibitor, an effective amount of an aliphatic or cycloaliphatic di-, tri- or tetra-carboxYlic acid which is substituted in its aliphatic or cycloaliphatic radical by at least one group of the formula I
s-R
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, -CN, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino or carbamoyl group, and aLso base addition salts of these compounds.
Depending on whether X is oxygen, sulfur or NH, these are derivatives of benzoxazole, benzthiazole or benzimidazole.
The benzthiazole derivatives are preferred.
As alkyl, alkoxy, alkylthio or alkylsulfonyl, R
preferably contains 1-12 C atoms, especially 1-6 C atoms.
Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl and the corresponding alkoxy, alkylthio and alkylsulfonyl radicals. As cycloalkyl, R
preferably contains 5-8 C atoms. Examples of these are cyclopentyl, cyclohexyl or cyclooctyl.
As halogenoalkyl, R preferably contains 1-4 C atoms and 1-3 fluorine or chlorine atoms. Examples of these are chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl or 2-chloroethyl~
As alkylphenyl, R preferably contains 7-16 C atoms and can be, for example, tolyl, xylyl, 4-isopropylphenyl, . .
. . . .
1 3 1 6 G ~ ~
4-tert.-butylphenyl, 4-octylphenyl or 4-decylphenyl. As phenylalkyl, R preferably conta;ns 7-9 C atoms and can be, for example, benzy(, 1-phenylethyl, 2-phenylethyl, a,-di-methylbenzyl or 3-phenylpropyl.
As halogen, R ;s preferably fluorine, chlorine or bromine. If R is -COOalkyl, the alkyl group preferably has 1-4 C atoms.
As an amino group or carbamoyl group, R preferably has up to 20 C atoms. Examples of these are the groups NH2~ -NHCH3, -NHC12H1s~ -NH-cyclohexyl, -NH-phenyl, -N~CH3)2, -N~C4Hg)2, -N~cH3)~benzyl)~ morpholino, piperidino, -CONH2, -CONHphenyl, -CONHCgH17, -CON~C2Hs)2, -C~N~CH2CH20H)2, morpholinocarbonyl or piper;dinocarbonyl.
Preferably, one of the substituents R is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or an amino group, and the other three Rs are hydrogen. It is part;cularly preferable for all four Rs to be hydrogen.
The component b) is preferably a d;carboxylic ac;d or a salt thereof. The substituent of the formula I is preferably in the beta-position in relation to a carboxyl group.
The component b) is preferably an aliphatic poly-carboxylic acid which has 2-20 C atoms or a cycloaliphatic polycarboxylic ac;d which has 4-12, in particular 5-8, C atoms and which is substituted by a group of the formula I. In addition to the group of the formula I, the carboxylic acid can also have other substituents, for example hydroxyl, alkoxy, halogen or aryl.
Components b) which are preferred are compounds of the formula II
`I/' ` ~ ~ II
1 31 6&~,5 in which X and R have the meaning g;ven above, n is zero or one and R1, R2, R3 and R4 indepPndently of one another are hydrogen, alkyl, hydroxyalkyl, halogenoalkyl, alkoxyalkyl, carboxyalkyl, carboxyl or phenyl or phenylalkyl which is unsubstituted or monosubstituted or disubstituted, or Ri and R2 or R1 and R3 together are linear or branched alky-lene which can be substituted by 1 or 2 carboxyl groups, or R1 and R2 together are a direct bond, and at least two of the substituents R1, R2, R3 and R4 are acarboxyl or car-boxyalkyl group, and also base addition salts of these compounds.
As alkyl, R1, R2, R3 and R4 are preferab~y ct-cl8-alkYl~ for example methyl, ethyl, n-propyl, isopro-pyl, n-butyl, isobutyl, tert.-butyl, pentyl, hexyl, octyl, dodecyl or octadecy~. As hydroxyalkyl or halogenoalkyl, these subst;tuents preferably have 1-4 C atoms. Examples of these are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, chloromethyl, bromoethyl or bromo;sopropyl. As alkoxyalkyl, these subst;tuents pre-ferably have 2-1û C atoms. Examples of these are methoxy-methyl, 1-methoxyethyl, 2-ethoxypropyl, 1-methoxybutyl, n-butoxymethyl or 4-isopropoxybutyl.
As carboxyalkyl, R1, R2, R3 and R4 are preferably C2-C12-carboxyalkyl, for example carboxymethyl, 1-carboxy-ethyl, 2-carboxyethyl, 3-carboxypropyl, 2-carboxy;sopropyl, 1-carboxybutyl, 2-carboxybutyl, 1-, 2- or 3-carboxyhexyl, 1,2-dicarboxyethyl or 2,3,4-tricarboxyl-1-butyl. As sub-stituted or unsubstituted phenyl or phenylalkyl, the same substituents can be, for example, 4-chlorophenyl, 3-nitro-phenyl, tolyl, xylyl, 3-methoxyphenyl, 4-isopropylphenyl, 3-carboxyethyl, 4-hydroxypheny~, 4-bromobenzyl, 4-tert.-butylbenzyl, 2-phenylethyl or 3-phenylpropyl, but are pre-ferably phenyl or benzyl.
~ f R1 and R2 or R1 and R3 together are alkylene, they form, together ~;th the C atoms to which they are linked, a cycloalkane ring, preferably a cyclopentane or cyclohexane ring, wh;ch can be substituted by alkyl groups, 1 31 6~')'',5 preferably ~1-C4-alkyl groups, or by 1 or 2 carboxyl groups.
If R1 and R2 together are a direct bond, the com-pounds of the formula II are unsaturated carboxylic acids.
R1, R2, R3 and R4 are preferably hydrogen, C1-C4-alkyl, carboxyl or C2-C6-carboxyalkyl. It ;s part;cularly preferable for R4 to be a carboxyl group.
Base addition salts are metal, ammonium or organic ammonium salts, ;n part;cular salts of alkal; metals, alka-line earth metals, metals of the groups tIB, IIIA or ~III
of the per;odic system of the elements, ammonium salts or salts of organ;c amines. Examples of these are, in par-ticular, sodium, potass;um, calcium, magnesium, zinc, alu-minium, ammonium, trialkylammonium and tris-thydroxyethyl)-ammonium salts.
The following are examples of corrosion inhibitors of the component b):
benzthiazol-2-ylthiomalonic acid, benzthiazol-2-ylth;osuccinic ac;d, 5-methylbenzth;azol-2-ylth;osuccinic acid, 6-ethylbenzth;azol-2-ylthiosuccinic acid, 4-;sopropylbenzth;azol-2-ylth;osucc;n;c acid, 7-t-butylbenzthiazol-2-ylthiosucc;n;c acid, 5-n-hexylbenzth;azol-2-ylthiosuccinic acid, 6-(1,1,3,3-tetramethylbutyl)-benzthiazol-2-ylth;osuccinic acid, 6-cyclohexylbenzthiazol-2-ylthiosuccinic acid, 1 31 66~5 7-benzylbenzth;azol-2-ylth;osuccinic acid, b-methoxybenzthiazol-2-ylthiosuccinic acid, ~S-ethoxybenzthiazol-2-ylthiosuccinic acid, 7-ethoxybenzthiazol-Z-ylth;osuccinic acid, 5-methoxybenzthiazol-2-ylthiosuccinic acid, 4-methylthiobenzthiazol-2-ylthiosuccinic acid, 4-fluorobenzthiazol-2-ylthiosuccin;c acid, 5-chlorobenzthiazol-2-ylthiosuccinic acid, 7-bromobenzth;azol-2-ylthiosuccinic acid, 6-chlorobenzthiazol-2-ylthiosuccinic acid, 4-phenylbenzthiazol-2-ylthiosuccinic acid, 5-trifluoromethylbenzthiazol-2-ylthiosuccinic acid, S-carboxybenzthiazoi-2-ylthiosuccinic ac;d, 6-methylsulfonylbenzthiazol-2-ylthiosuccinic acid, 5-cyanobenzth;azol-2-ylthiosuccinic acid, 6-n;trobenzth;azol-2-ylth;osuccin;c ac;d, S-cyanobenzthiazol-2-ylthiosuccin;c acid, 7-hydroxybenzthiazol-2-ylthiosucc;nic acid, 6-chloro-4-methylbenzth;azol-2-ylthiosucc;nic acid, S-chloro-6-n-butylbenzthiazol-2-ylthiosuccinic acid, 4-bromo-5-n-hexylbenzthiazol-2-ylthiosuccinic acid, 5-nitro-6-n-propylbenzthiazol-2-ylthiosuccinic acid, S-bromo-6-n-propoxybenzthiazol-2-ylthiosuccinic acid, 6-aminobenzthiazol-2-ylthiosuccinic acid, 6-methylaminobenzthiazol-2-ylthiosuccinic acid, 5-dimethylaminobenzth;azol-2-ylth;osucc;n;c ac;d, 7-phenylaminobenzthiazol-2-ylthiosuccinic acid, 6-diphenylaminobenzthiazol-2-ylthiosuccinic acid, 4-benzylaminobenzthiazol-2-ylth;osuccinic acid, 4-morpholinobenzth;azol-2-ylth;osucc;nic acid, 5-carbamoylbenzthiazol-2-ylthiosuccin;c acid, 5-methylcarbamoylbenzth;azol-2-ylthiosuccin;c acid, S-diethylcarbamoylbenzthiazol-2-ylthiosucc;n;c acid, 6-phenylcarbamoylbenzth;azol-2-ylthiosuccinic acid, 5,6-dimethylbenzthiazol-2-ylth;osucc;nic acid, 4,5,6-triethylbenzth;azol-2-ylth;osuccinic acid, 4,5,6,7-tetramethylbenzth;azol-2-ylthiosucc;n;c acid, - 8 - 13~ 6~
1-(benzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(6-trifluoromethylbenzthiazol-2-ylthio)-proPane-1,2-di-carboxylic acid, 3-(6-methoxycarbonylbenzthiazol-2-ylthio)-propane-1,2-di-carboxylic acid, 3-(6-aminobenzthiazol-2-ylthio)~propane-1,2-dicarboxylic acid, 3-(5-ethylaminobenzth;azol-2-ylthio)-propane~1,2~dicarboxy-l;c ac;d, 3-(4-dibutylaminobenzthiazol-2-ylth;o)-propane-1,2-dicar-boxylic ac;d, 4-(morphol;nobenzth;azol-2-ylthio)-propane-1,2-dicarboxylic ac;d, 1-(4-phenylbenzth;azol-2-ylth;o)-propane-1,2-dicarboxylic ac;d, 1-~benzth;azol-2-ylth;o)-propane-1,3-dicarboxylic acid, 1-(6-ethylbenzth;azol-2-ylth;o)-propane-1,3-d;carboxylic acid, 2-(benzthiazol-2-ylthio)~propane-1,3-dicarboxylic acid, 2-(5-carboxybenzthiazol-2-ylthio)-propane-1,3-dicarboxylic ac;d, 3-(benzthiazol-2-ylthio)-3-phenylpropane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-3-(4-carboxyphenyl)-propane-1,2-dicarboxyl;c acid, 3-(benzthiazol-2-ylth;o)-3-(2,4-d;carboxylphenyl)-propane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-3,3-diphenylpropane-1,2-dicarboxy-l;c ac;d, 1-(benzthiazol-2-ylthio)-butane-1,2-dicarboxyl;c acid, 1-~4-methoxy-6-hydroxybenzthiazol-2-ylthio)-butane-1,2-di-carboxylic acid, 3-(4,5-dimethyl-7-propoxybenzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(benzthiazol-2-ylthio)~2-methylpropane~1,2~dicarboxylic acid~
:. -_ 9 _ 2-tbenzthiazol-2-ylthio)-butane-2,3-dicarboxyl;c acid~
1-~benzthiazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-(benzthiazol-2-ylthio)-butane-1,2,3-tricarboxylic acid, 4-(benzthiazol-2-ylthio)-butane~1,4-dicarboxylic acid, 1-(benzthiazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-hexane~1,2~dicarboxylic acid, 8-(benzthiazol-2-ylthio)-octane-1,3,5,7~tetracarboxylic acid, 1-(benzthiazol-2-ylthio)-cyclohexane~1,2-dicarboxylic acid, ~-(benzthiazol-2-ylthio)-cyclohexane~1,2-dicarboxylic ac;d, 1-(benzth;azol-2-ylthio)-propane-1,2,3-tricarboxylic acid, 1-(benzthiazol-2-ylthio)-3-chloropropane-1~2~dicarboxylic acid, 1-(benzth;azol-2-ylthio)-3-methoxypropane-1,2-dicarboxylic acid, 1-(benzthiazol-2-ylthio)-3-hydroxypropane-1,2-dicarboxylic ac;d, 1-(benzth;azol-2-ylth;o)-2-phenylsucc;nic acid, 1-(benzthiazol-2-ylthio)-2-benzylsucc;nic acid, 1-~benzthiazol-2-ylthio)-3-methylbutane-1,3-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-hexane-3,4-dicarboxylic acid, 2,3-bis-~benzthiazol-2-ylthio)-butane-1,4-dicarboxylic acid, disodium benzthiazol-2-ylthiosuccinate, dlpotassium benzthiazol-2-ylthiosuccinate, calcium benzthiazol-2-ylthiosuccinate, zinc benzthiazol-2-ylthiosuccinate, cobalt benzthiazol~2~ylthiosuccinate, alumin;um benzthiazol-2-ylthiosuccinate, ammon;um benzth;azol-2-ylth;osuccinate, bis-methylammonium benzthiazol-2-ylthiosuccinate, bis-triethanolammon;um benzth;azol-2-ylthiosuccinate, b;s-octylammonium benzth;azol-2-ylth;osuccinate, bis-cyclohexylammonium benzthiazol-2-ylthiosuccinate, diethylammonium benzthiazol-2-ylthiosuccinate, tributylam~onium benzthiazol~2~ylthiosuccinate, 1 ~1 66~
d;sodium 3-(benzthiazol-2-ylthio)~propane-1,2-dicarboxylate, dipotassium 3-(benzthiazol~2~ylthio)~propane-1,2~dicarboxy~
late, calcium 3-~benzthiazol-2-ylthio)-propane-1,2-dicarboxy-late, zinc 3-(benzthia2ol-2-ylthio)-propane-l~2-dicarboxylate~
aluminium 3-(benzthiazol~2-ylthio)-propane-1,2-dicarboxy-late, ammonium 3-(benzth;azol-2-ylthio)-propane~1,2~dicarboxy-late, bis-methylammon;um 3-(benzthiazol-2-ylthio)-propane-1,2-d;-carboxylate, bis-(tr;ethanolammonium) 3-(benzth;azol-2-ylthio)-propane-1,2-dicarboxylate, benzoxazol-2-ylthiomalon;c acid, benzoxazol-2-ylth;osucc;n;c acid, 5-methylbenzoxazol-2-ylth;osùcc;nic acid, 6-ethylbenzoxazol-2-ylth;osucc;nic ac;d, 4-;sopropylbenzoxazol-2-ylth;osucc;nic acid, 7-t-butylbenzoxazol-2-ylth;osucc;n;c ac;d, 5-n-hexylbenzoxazol-2-ylth;osucc;n;c ac;d, 6-C1,1,3,3-tetramethylbutyl~-benzoxazol-2-ylthiosucc;n;c ac;d, 6-cyclohexylbenzoxazol-2-ylth;osucc;n;c ac;d, ~-benzylbenzoxazol-2-ylth;osucc;n;c ac;d, 6-methoxybenzoxazol-2-ylth;osucc;n;c acid, 7-ethoxybenzoxazol-2-ylthiosuccinic ac;d, 1 31 6~S5 6-ethoxybenzoxazol-2-ylthiosucc;nic acid, S-methoxybenzoxazol-2-ylthiosuccinic acid, S-ethoxycarbonylbenzoxazol-2-ylthiosuccinic acid, 4-methylthiobenzoxazol-2-ylthiosuccinic acid, 6-methylsulfonylbenzoxazol-2-ylthiosuccinic acid, 4-fluorobenzoxazol-2-ylthiosuccinic acid, S-chlorobenzoxazol-2-ylthiosuccinic acid, 7-bromobenzoxazol-2-ylthiosuccinic ac;d, 6-chlorobenzoxazol-2-ylthiosuccinic acid, 4-phenylbenzoxazol-2-ylth;osucc;n;c acid, 6-nitrobenzoxazol-2-ylthiosuccin;c ac;d, 5-cyanobenzoxazol-2-ylth;osuccinic acid, S-carboxybenzoxazol-2-ylthiosuccinic acid, 7-hydroxybenzoxazol-2-ylthiosuccin;c acid, 6-chloro-4-methylbenzoxazol-2-ylth;osuccinic acid, 5-chloro-6-n-butylbenzoxazol-2-ylth;osuccinic acid, 4-bromo-5-n-hexylbenzoxazol-2-ylth;osuccinic ac;d, S-nitro-6-n-propylbenzoxazol-2-ylth;osucc;n;c acid, 5-bromo-6-n-propoxybenzoxazol-2-ylth;osucc;nic ac;d, 6-am;nobenzoxazol-2-ylth;osucc;n;c ac;d, 6-methylam;nobenzoxazol-2-ylth;osucc;nic acid, S-d;methylaminobenzoxazol-2-ylthiosuccinic acid, 7-phenylam;nobenzoxazol-2-ylthiosuccinic acid, 6-diphenylaminobenzoxazol-2-ylth;osuccinic acid, 4-benzylaminobenzoxazol-2-ylthiosuccinic acid, 4-morpholinobenzoxazol-2-ylthiosuccinic acid, 5-carbamoylbenzoxazol-2-ylthiosuccinic acid, S-methylcarbamoylbenzoxazol-2-ylthiosuccinic acid, S-diethylcarbamoylbenzoxazol-2-ylthiosuccinic acid, 6-phenylcarbamoylbenzoxazol-2-ylthiosuccinic acid, 5,6-dimethylbenzoxazol-2-ylthiosuccinic acid, 4,5,6-triethylbenzoxazol-2-ylthiosuccinic acid, 4,5,6,7-te~ramethylbenzoxazol-2-ylthiosuccin;c acid, 1-(benzoxazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(4-phenylbenzoxazol-2-ylthio)-propane-1,2-dicarboxyl;c acid, 3-~benzoxazol-2-ylthio~-propane-1,2-d;carboxylic acid, 1 31 66~,5 3-(6-tr;fluoromethylbenzoxazol-2-ylthio)-propane-1-2-dicar-boxylic acid, 3-(6-methoxycarbonylbenzoxazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 3-(6-aminobenzoxazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(5-ethylaminobenzoxazol-2-ylthio)-propane-1,2-dicarboxy-lic acid, 3-(4-dibutylaminobenzoxazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 4-tmorpholinobenzoxazol-2~ylthio)~propane~1,2~dicarboxylic acid, 1-(benzoxazol-2-ylthio)-propane-1,3-dicarboxylic acid, 1-~6-ethylbenzoxazol-2-ylthio)-propane-1,3-dicarboxylic acid, 2-~benzoxazol-2-ylthio)-propane-1,3-d;carboxylic acid, 2-~5-carboxybenzoxazol-2-ylth;o)-propane-1,3-dicarboxylic acid, 3-(benzoxazol-2-ylth;o~-3-phenylpropane-1,2-d;carboxylic acid, 3-(benzoxazol-Z-ylth;o)-3-(4-carboxyphenyl~-propane-1,2-di-carboxylic ac;d, 3-(benzoxazol-2-ylthio~-3-(2,4-dicarboxyphenyl)-propane-1,2-dicarboxylic acid, 3-(benzoxazol-2-ylthio)-3,3-diphenylpropane-1,2-dicarboxy-l;c acid, 1-(benzoxazol-2-ylthio)-butane-1,2-dicarboxylic acid, 1-(4-methoxy-6-hydroxybenzoxazol-2-ylthio)-butane-1,2-di-carboxylic acid, 3-(4,5-dimethyl-7-propoxybenzoxazol-2-ylthio~-propane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio~-2-methylpropane-1,2-d;carboxylic acid, 2-(benzoxazol-2-ylthio)-butane-2,3-dicarboxylic acid, 1-(benzoxazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-~benzoxazol-2-ylthio~-butane-1,2,3-tricarboxylic acid, 4-(benzoxazol-2-ylthio)-butane-1,4-dicarbo%ylic acid, 1 31 66~,5 1-~benzoxazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benzoxazol-2-ylthio)-hexane-1,2-dicarboxylic asid, ~-(benzoxazol-2-ylthio)-octane-1,3,5,7-tetracarboxylic acid, 1-(benzoxazol-2-rlthio)-cyclohexane-1,2-dicarboxylic acid, 4-(benzoxazol-2-ylthio)-cyclohexane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio)~propane-1,2,3-tricarboxylic acid, 1-(benzoxazol-2-ylthio)~3~chloropropane-1,2-dicarboxylic acid, 1-~benzoxazol-2-ylthio)-3-methoxypropane-1,2~dicarboxylic acid, 1-(benzoxazol-2-ylthio)-3-hydroxypropane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio)-2-phenylsucçinic acid, 1-~benzoxazol-2-ylthio)-2-benzylsuccinic acid~
1-tbenzoxazol-2-ylth;o)-3-methylbutane-1,3-dicarboxylic acid, 3-~benzoxazol-Z~ylthio)~hexane-3,4~dicarboxyl;c acid, 2,3-bis-~benzoxazol-2-ylthio)-butane-1,4-dicarboxylic acid, disodium benzoxazol-2-ylth;osuccinate, dipotassium benzoxazol-Z-ylthiosuccinate, calcium benzoxazol-2-ylthiosuccinate, zinc benzoxazol-2-ylthiosuccinate, cobalt benzoxazol-2-ylthiosuccinate, ammonium benzoxazol-2-ylthiosuccinate, bis-methylammonium benzoxazol-2-ylthiosuccinate, bis-triethanolammonium benzoxazol-2-ylthiosuccinate, bis-octylammon;um benzoxazol-2-ylthiosuccinate, bis-cyclohexylammonium benzoxazol-2-ylthiosuccinate, diethylammoniùm benzoxazol-2-ylthiosuccinate, tributylammonium benzoxazol-2 ylthiosucc;nate, disodium 3-(benzoxazbl-2-ylthio)-propane-1,2-dicarboxylate, dipotassium 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxy-late, calcium 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxyLate, zinc 3-(benzoxazol-2-ylthio~-propane-1,2-dicarboxylate, ammon;um 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxylate, 1 31 66'',5 bis-methylammonium 3-(benzoxazol-2-ylthio)~Propane-l~2-d carboxyLate, b;s-triethanoLammonium 3-~benzoxazoL-2-yLthio)~Propane-l,Z-dicarboxylate, benzimidazol-2-ylthiomalon;c acid, benzimidazol-2-ylthiosuccinic acid, 5 (or 6)-methylbenzim;dazol-2-ylth;osuccinic acid, 6 (or 5)-ethylbenzimidazol-2-ylthiosuccin;c acid, 4 (or 7)-isopropylbenzimidazol-2-ylthiosuccinic acid, ? tor 4)-t-butylbenz;midazol-2-ylth;osucc;nic acid, S ~or 6)-hexylbenzim;dazol-2-ylth;osuccin;c acid, 6 (or S)-Ct,1,3,3-tetramethylbutyl~-benzimidazol-2-ylthio-succinic acid, 7 (or 4)-benzylbenzimidazol-2-ylthiosuccinic acid, 6 (or 5)-methoxybenzimidazol-2-ylthiosuccinic acid, 5-ethoxycarbonylbenzimidazol-2-ylthiosuccinic acid, 6 (or 5)-ethoxybenzimidazol-2-ylth;osucc;n;c ac;d, 7 ~or 4)-ethoxybenzimidazol-2-ylthiosuccinic acid, 4 (or 7)-fluorobenzimidazol-2-ylthiosuccinic acid, 5 tor 6)-chlorobenz;midazol-2-ylthiosuccinic acid, 7 (or 4)-bromobenzim;dazol-2-ylthiosuccin;c acid, 6 ~or 5)-nitrobenzimidazol-2-ylthiosuccinic acid, S ~or 6)-methylsulphonylbenz;midazol-2-ylthiosuccin;c acid~
1-(benzimidazol-2-ylthio)-2-phenylsuccinic acid, S (or 6)-chloro-4 (or 7)-methylbenzimidazol-2-ylthiosuc-cinic acid, 1 31 66~5 , 5 S (or 6)-chloro-6 tor 5)-n-butylbenzimidazol-2-ylth;osuc-cinic acid, 4 tor 7)-bromo-5 (or 6)-n-hexylbenzimidazol-2-ylthiosuc-cinic acid, S (or 6)-nitro-6 tor 5)-n-propylbenzimidazol-2-ylthiosuc-cinic acid, 5 tor 6)-bromo-6 (or 5)-n-propoxybenzimidazol-2-ylthiosuc-cinic acid, 5,6-dimethylbenzimidazol-2-ylthiosuccinic acid, 4,5,6-triethylbenzimidazol-2~ylthiosuccinic acid, 4,5,6,7-tetramethylbenzim;dazol~2~ylthiosuccinic acid, 5 (or 6)-aminobenzimidazol-2-ylthiosuccinic acid, t1- benzim;dazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(4 (or 7)-phenylbenzim;dazol-2-ylthio)-propane-1,2-dicar-boxyl;c ac;d, 1-(benz;m;dazol-2-ylth;o)-propane-1,3-dicarboxyl;c acid, 1-(6 (or 5)-ethylth;obenzim;dazol-2-ylth;o)-propane-1,3-di-carboxyl;c ac;d, 2-(benzimidazol-2-ylthio)-propane-1,3-dicarboxylic acid, 2-t5 (or 6)-carboxybenzim;dazol-2-ylthio)-propane-1,3-di-carboxyl;c ac;d, 3-tbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(5 (or 6)-aminobenzimidazol-2-ylthio)-propane-1,2-dicar-boxyl;c acid, 3-t5 tor 6)-ethoxycarbonylbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-t5 tor 6)-trifluoromethylbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(4 (or 7)-dipropylaminobenzimidazol-2-ylthio)-propane-1,2-dicarboxylic ac;d, 3-(4 (or 7~-morphol;nobenz;midazol-2-ylth;o)-propane-1,2-dicarboxylic acid, 3-(5 (or 6)-carbamoylbenzimidazol-2-ylthio)-propane-1,2-di-carboxylic ac;d, 3-(4 tor 7)-cyanobenzim;dazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 3-(benzim;dazol-2-ylthio)-3-phenylpropane-1,2-dicarboxylic 1 31 6G',5 - ~6 -acid, 3-(benzimidazol-2-ylthio)-3-(4-carboxyphenyl)-propane-1,2-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-3-~2,4-dicarboxyphenyl)-propane-1,2-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-3,3-diphenylpropane-1,2-dicar-boxylic acid, 1-~benzimidazol-2-ylthio)-butane-1,2-dicarboxylic acid, 1-~4 (or 7)-methoxy-6 (or 5)-hydroxybenzimidazol-2-ylthio)-butane-1,2-dicarboxylic acid, 4-(benz;midazol-2-ylthio)-butane-1,2,3-tr;carboxylic acid, 1-(4 (or 7)-methyl-7 ~or 4)-propoxybenzimidazol-2-ylthio)-propane-2,3-dicarboxylic acid, 1-(benzimidazol-2-ylth;o)-2-methylpropane-1,2-dicarboxylic acid, 2-(benzimidazol-2-ylthio)-butane-2,3-dicarboxylic acid, 1-(benz;midazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-(benz;m;dazol-2-ylth;o)-butane-1,4-dicarboxyl;c acid, 1-~benzimidazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benz;midazol-2-ylth;o)-hexane-1,2-d;carboxylic acid, 8-(benzim;dazol-2-ylthio)-octane-1,3,5,7-tetracarboxylic ac;d, 1-~benzimidazol-2-ylthio)-cyclohexane-1,2-dicarboxylic ac;d, 4-(benzimidazol-2-ylthio)-cyclohexane-1,2-dicarboxylic acid, 1-~benzimidazol-2-ylthio)-propane-1,2,3-tricarboxylic acid, 1-(benzimidazol-2-ylthio)-3-chloropropane-1,2-dicarboxylic acid, 1-~benzimidazol-2-ylthio)~3-methoxypropane-1,2~dicarboxylic ac;d, 1-(benzimidazol-2-ylthio)-3-hydroxypropane-1,2-d;carboxylic acid, 1-(benzimidazol-2-ylthio)-3-methylbutane-1,3-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-hexane-3,4-dicarboxylic acid, disodium benzimidazol-2-ylthiosuccinate, dipotassium benzimidazol-2-ylthiosuccinate, 1 31 66~ ~
calc~um ben2imida20l-2-ylthiosuccinate, 2~nc benzlmidazol-2-ylthiosuccinate, cobalt ben2imidazol-2-ylthiosuccinate, ammonium benz~midazol-2-ylthiosuccinate, b1s-methylammon1um benz~midazol-2-ylthiosuccinate, b1s-triethanolammonium benzim1dazol-2-ylthiosuccinate, bis-octylammonium benzim~dazol-2-ylthiosuccinate, bis-cyclohexylammon~um benzlmida20l-2-ylthiosuccinate and d;ethylammonium ben21m1dazol-2-ylthiosuccinate.
tO The compounds of the formula II which are used ln accord~nce uith the ~nventlon as corros~on 1nhlb1-tors are knoun compound ; The preparatlon of the compounds tan be effected in accordance u~th a proces~ of European Patent Applicat~on Publ.
No. 129506, by reactlng a compound of the formula III
R\t~ ~./ ~ III
R
ln uhlch A ls a leavlng group, for example Cl, Or, I or p-tosyloxy, ulth a compound ot the tormula ~R
1n ~h~ch 11 ~s hydrogen or a catlon, for example an alkall metal cat10n, ~lkallne earth metal cat~on or ammon~um cat-20 lon. Alternativelr, a compound of the formula IV
1316~ 5 I ll ~ -S-M IV
R ~ ~
can be reacted with a compound of the formula Compounds of the formula ~I in which X ;s sulfur or NH and R4 ;s carboxyl can aLso be prepared by reacting IV, ;n wh;ch M ;s hydrogen and X is S or NH, with an a, ~-un-saturated ac;d o~ the formula l 2 =c~
R COOH
in accordance with a process which ;s the subject of Europ. Patent Application Publ. No. 126030.
The component a) can be any des;red film-former, such as those wh;ch are known as binders for aqueous coating compGs;tions e.g. dispersion paints, emulsion paints or electrodepositable paints. The aqueous binder used as component a) may be one or more water-soluble or water-dispersible synthetic polymer. Examples of such polymers are alkyd, polyester, acrylic, polyurethane, epoxide, phenoplast or aminoplast resins and mixtures of these resins,and homo- or copolymers of vinyl ethers, vinyl esters, styr-ene, vinylidene chloride and v;nyl chloride.
The water-borne binder may be optionally crosslinked with aminoplast resins, phenoplast resins, blocked isocyanates, epoxy resins, Mannic h bases of phenols or activated carboxylic esters.
: -1 3 1 66~,5 There are several methods available for rendering these binders suitable for use in water-borne paints. These methods, which are well known to those skilled in the coatings art, include the incorporation of basic or acidic functional groups which are then neutralised prior to d;lution with water~
In addition to the components a) and b), the coat-ing composition can also contain further components, for example pigments, dyes, extenders and other additives such as are customary for water-borne coating compositions. The pigments can be organic, inorganic or metallic pigments, for example titanium dioxide, iron oxide, aluminium bronze, phthalocya-nine blue etc. It is also possible to use concomitantly anti-corrosion pigments, for example pigments containing phosphates or borates, metal pigments and metal oxide pig-ments (see Farbe und Lack 88 (1982), 183) or the ~igments described in European Patent A 54,267. Examples of exten-ders hhich can be used concomitantl~ are talc, chalk, alu-mina, baryte, mica or silica. ~xamples of 'urtner addi-tives are flow control auxiliaries, dispersing agents, th;xotropic agents, adhesion promoters, an.ioxidants, light stabilisers or curing catalysts.
Particular importance attaches to the addi;ion of basic extenders or pigments. In certain binder systems, for example in acrylic and alkyd resins, these produce a synergistic effect on the inhibition of corrosion.
Examples of such basic extenders or pigments are calcium carbonate, magnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, aluminium oxide, aluminium phosphate or mixtures thereof. Examples of pigments are those based on aminoanthraquinone.
The corrosion inhibitors according to the invention can also first be applied to such basic extenders or pig-ments, for example by chemisorption from an aqueous solu-tion, and the preparations thus obtained can be added to the coating composition.
1 31 66~5 In a further preferred embodiment of the invention the corrosic,n inh;bitors are used together ~ith basic ion exchangers or an ion exchanger of this type is first treated with a solution of the inhibitor, and this prepara-tion is then added to the coat;ng compos;tion. Examples of basic ion exchangers are all typical anion exchangers, such as those available commercially, for example under the names Dowex R 1 or 11 or Amberlite R IRA.
Finally, the corrosion inhibitor can also be app-lied to a neutral carrier. Suitable carriers are, in par-ticular, pulverulent extenders or pigments. This technique is described in greater detail in German Offenlegungs-schrift 3,122,907.
In addition to the component b), the coating composition can also contain another organic, metal-organic or inorganic corrosion inhibitor, for exam?le salts of nitro;sophthalic acid, tannin, phosphoric esters, technical amines, substituted benztriazoles or subs~ituted phenols, such as are described in German Offenlegungsschrift 3,146,~65~
The coating compositions according to the invention are preferably used as a primer on metallic substrates, in particular on iron, steel, copper and aluminium. Here they can function as so-called conversion coa;ings, in that chemical reactions take place at the interface ~etween the metal dn the coating. The coating compositions may also find application ;n can coating processes. The application of the coatings can be effected by the customary methods, such as spraying, brushing, roller-coating or dipping.
One preferred method is electrodeposition which may be either anodic or cathodic, but is preferably cathodic.
1 3 1 6 6 ~
Depending on whether the film-former is a resin which dries phys;cally or can be cured by heat or radiation, t~e cur;ng of the coatings is carried out at room temperature, by stoving or by irradiation.
The corrosion inhibitors can be added to the coat-ing composition during the preparation of the latter, for example during the distribution of the pig~ent by grinding or the ;nhibitors are dissolved beforehand in a solvent and the solution is stirred into the coating composition. The innibitor is used in an amount of û.1 - 2û,. by ~eight, pre-ferably û.5 - 5,'. by weight, based on the solids content of the ~o~tinq composition.
Example_ A water-based maintenance primer is prepared by mixing the follow;ng components (A) and (B) ~A) Pigment Paste 14.6 9 TiO2-Pigment (Ti-Pure ~ R-96û, Du Pont de Nemours Co) 1.4 9 35 % aqueous solution of an dispersing agent (Dispersing Agent QR 681 M, Rohm & Haas) 0.2 g pigment wetting agent (Triton ~ CF 10, Rohm & Haas) 4.7 9 dist. water 0.2 9 antifoaming agent (Colloids 643, Colloids Inc.) 1.2 9 zinc oxide 5.1 9 micronized CaC03 (Millicarb ~ , Pluss-Staufer) 27.4 9 1 31 6~5 ~B) Binder Dispers;on 64.4 9 43 % aqueous dispersion of an acrylic resin tPrimal ~ MV 23, Rohm & Haas) 1.0 g 2-butoxyethoxy-ethanol 2.7 9 ethylene glycol 0.2 9 mildewcide agent CSkane ~ M-8, Rohm & Haas) 0.4 9 antifoaming agent (Colloids 643, Colloids Inc.) 0.2 9 thickener (Primal ~ ICS-1, Rohm & Haas) 1.1 9 rheology modifier (Primal ~ RM-8, Rohm & Haas) 2.6 9 dist. water 72.6 9 The mixed primer has a solid content of 48 %. To this dispersion are added the corrosion inhibitors indicated in the follow;ng table.
The primer is applied to phosphatised iron sheets in a thickness of 100~um. The samples are baked at 130C for 20 m;nutes and are afterwards tested by a salt spray test according to ASTM method B-117 for a duration of 600 hours.
The condition of the coating is assessed at the cross-cut and on 'he whole surface according to DIN methods 53 209 and 53 210.
The coating is removed by treatment with concentrated NaOH
solution and the corrosion of the metal is assessed according to DIN method 53 167. In both cases the assessment is made on the basis of a 6-stage scale.
The sum of the assessment of coating and metal is the corrosion protection ~alue ~CP).
i. , I
1 3 1 6 6 ~ ' *) Assessment Assessment Corrosion Inhibitor Amount of coating of metal CP
-none - 3.6 3.9 7.5 Benzthiazol-2-ylthio-succinic acid-zinc salt 2 % 3.7 4.3 8.0 -NH4 salt 2 % 4.1 4.3 8.4 3 % 4.3 5.2 9.5 3-~Benzthiazol-2-ylthio)-propane-1,2-dicarboxylic ac;d-NH4 salt 5 % 4.4 4.5 8.9 ) related to the solid coating
Corrosion-inhibiting aqueous coat;ng compositions The present invention relates to aqueous coating compositions which, by virtue of containing certain compounds, are capable of inhibiting the corrosion of metallic sub-strates, especially ferrous metals. The compounds are aliphat;c or cycloaliphatic carboxylic acids containing a heterocyclic radical.
Protection against corrosion is one of the most important duties of organic coating compositions for metal substrates. Many suggestions for improving the protection of coatings against corrosion are to be found in the litera-ture, for example in H. Kittel, Lehrbuch der Lacke und Be-schichtungen ("Textbook of Paints and Coatings"), volume V, Stuttgart l977, 46-103. On the one hand, the barrier function of the coating composition can be improved, in order to keep corrosive agents, such as oxygen, water and ions, away from the metal surface~ On the other hand, it is possible to employ corrosion-inhibiting pigments which intervene chemically or electrochemically in the corrosion process, for example by the formation of insoluble deposits with corrosion products or by passivation (polarisation~ of the metal surface. Metal chromates and lead compounds rank amongst the most effective corrosion-inhibiting pigments. Much use has been made of metal chromates, particularly because they inhibit both anodic and cathodic corrosion. Nowadays there are certain objections to the use of chromates owing to their potential carcinogenic action. Similarly, there are objections to the use of lead compounds owing to their chronic toxicity.
Metal salts of organic compounds have also been frequently suggested as corrosion inhibitors. Thus, for example, European Patent Specification 3,817 recommends the use of zinc or lead salts of hydroxy or mercapto compounds of 5-membered or 6-membered heterocyclic compounds containing the characteristic group ~ 1 3 1 6 6 ~?~
-N=gH or -N=~-Typical examples of these are the Zn or Pb salts of 2-mer-captobenzthiazole.
In a separate patent Application, certain heterocyclic carboxylic acids and salts thereof have been described which can be used as corrosion inhibitors for coating compositions, which makes it possible to formulate highly effective corrosion-inhibiting paints which are free from chromates and lead.
Organic corrosion inhibitors of this type are not pigments, and their use in coating compositions therefore permits a free choice of pigments or extenders. In the fieLd of coating composit;ons, however, here has hitherto been doubt whether the addition of organic corrosion inhibitors on their own makes possible adequate protection, in practice, against corros;on (Farbe und Lack _ ~1981) 787).
The tw;n factors of env;ronment protection and of economy of natural resources are fundamental to any modern chemical manufacture. In the case of surface coatings manufacture, these factors have influenced a trend away from the expensive, hazardous and polluting hydrocarbon solvents towards water-borne coatings.
It has now been found that certain heterocyclic carboxylic ac;ds and their salts are effective corrosion inhibitors in such water-borne coatings.
It is surprising, therefore, that the organic corrosion inhibitors used according to the invention have a corrosion-inhibit;ng effect in aqueous coat;ng compos;tions which is in certain cases equal to that of chromate or lead pigments, or even surpasses the latter.
The present invention relates, therefore, to an aqueous corrosion-inhibiting coating composition containing a) an aqueous film-form;ng b;nder and .. . .
1 3 1 66~5 b) as the corrosion inhibitor, an effective amount of an aliphatic or cycloaliphatic di-, tri- or tetra-carboxYlic acid which is substituted in its aliphatic or cycloaliphatic radical by at least one group of the formula I
s-R
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, -CN, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino or carbamoyl group, and aLso base addition salts of these compounds.
Depending on whether X is oxygen, sulfur or NH, these are derivatives of benzoxazole, benzthiazole or benzimidazole.
The benzthiazole derivatives are preferred.
As alkyl, alkoxy, alkylthio or alkylsulfonyl, R
preferably contains 1-12 C atoms, especially 1-6 C atoms.
Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl and the corresponding alkoxy, alkylthio and alkylsulfonyl radicals. As cycloalkyl, R
preferably contains 5-8 C atoms. Examples of these are cyclopentyl, cyclohexyl or cyclooctyl.
As halogenoalkyl, R preferably contains 1-4 C atoms and 1-3 fluorine or chlorine atoms. Examples of these are chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl or 2-chloroethyl~
As alkylphenyl, R preferably contains 7-16 C atoms and can be, for example, tolyl, xylyl, 4-isopropylphenyl, . .
. . . .
1 3 1 6 G ~ ~
4-tert.-butylphenyl, 4-octylphenyl or 4-decylphenyl. As phenylalkyl, R preferably conta;ns 7-9 C atoms and can be, for example, benzy(, 1-phenylethyl, 2-phenylethyl, a,-di-methylbenzyl or 3-phenylpropyl.
As halogen, R ;s preferably fluorine, chlorine or bromine. If R is -COOalkyl, the alkyl group preferably has 1-4 C atoms.
As an amino group or carbamoyl group, R preferably has up to 20 C atoms. Examples of these are the groups NH2~ -NHCH3, -NHC12H1s~ -NH-cyclohexyl, -NH-phenyl, -N~CH3)2, -N~C4Hg)2, -N~cH3)~benzyl)~ morpholino, piperidino, -CONH2, -CONHphenyl, -CONHCgH17, -CON~C2Hs)2, -C~N~CH2CH20H)2, morpholinocarbonyl or piper;dinocarbonyl.
Preferably, one of the substituents R is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or an amino group, and the other three Rs are hydrogen. It is part;cularly preferable for all four Rs to be hydrogen.
The component b) is preferably a d;carboxylic ac;d or a salt thereof. The substituent of the formula I is preferably in the beta-position in relation to a carboxyl group.
The component b) is preferably an aliphatic poly-carboxylic acid which has 2-20 C atoms or a cycloaliphatic polycarboxylic ac;d which has 4-12, in particular 5-8, C atoms and which is substituted by a group of the formula I. In addition to the group of the formula I, the carboxylic acid can also have other substituents, for example hydroxyl, alkoxy, halogen or aryl.
Components b) which are preferred are compounds of the formula II
`I/' ` ~ ~ II
1 31 6&~,5 in which X and R have the meaning g;ven above, n is zero or one and R1, R2, R3 and R4 indepPndently of one another are hydrogen, alkyl, hydroxyalkyl, halogenoalkyl, alkoxyalkyl, carboxyalkyl, carboxyl or phenyl or phenylalkyl which is unsubstituted or monosubstituted or disubstituted, or Ri and R2 or R1 and R3 together are linear or branched alky-lene which can be substituted by 1 or 2 carboxyl groups, or R1 and R2 together are a direct bond, and at least two of the substituents R1, R2, R3 and R4 are acarboxyl or car-boxyalkyl group, and also base addition salts of these compounds.
As alkyl, R1, R2, R3 and R4 are preferab~y ct-cl8-alkYl~ for example methyl, ethyl, n-propyl, isopro-pyl, n-butyl, isobutyl, tert.-butyl, pentyl, hexyl, octyl, dodecyl or octadecy~. As hydroxyalkyl or halogenoalkyl, these subst;tuents preferably have 1-4 C atoms. Examples of these are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, chloromethyl, bromoethyl or bromo;sopropyl. As alkoxyalkyl, these subst;tuents pre-ferably have 2-1û C atoms. Examples of these are methoxy-methyl, 1-methoxyethyl, 2-ethoxypropyl, 1-methoxybutyl, n-butoxymethyl or 4-isopropoxybutyl.
As carboxyalkyl, R1, R2, R3 and R4 are preferably C2-C12-carboxyalkyl, for example carboxymethyl, 1-carboxy-ethyl, 2-carboxyethyl, 3-carboxypropyl, 2-carboxy;sopropyl, 1-carboxybutyl, 2-carboxybutyl, 1-, 2- or 3-carboxyhexyl, 1,2-dicarboxyethyl or 2,3,4-tricarboxyl-1-butyl. As sub-stituted or unsubstituted phenyl or phenylalkyl, the same substituents can be, for example, 4-chlorophenyl, 3-nitro-phenyl, tolyl, xylyl, 3-methoxyphenyl, 4-isopropylphenyl, 3-carboxyethyl, 4-hydroxypheny~, 4-bromobenzyl, 4-tert.-butylbenzyl, 2-phenylethyl or 3-phenylpropyl, but are pre-ferably phenyl or benzyl.
~ f R1 and R2 or R1 and R3 together are alkylene, they form, together ~;th the C atoms to which they are linked, a cycloalkane ring, preferably a cyclopentane or cyclohexane ring, wh;ch can be substituted by alkyl groups, 1 31 6~')'',5 preferably ~1-C4-alkyl groups, or by 1 or 2 carboxyl groups.
If R1 and R2 together are a direct bond, the com-pounds of the formula II are unsaturated carboxylic acids.
R1, R2, R3 and R4 are preferably hydrogen, C1-C4-alkyl, carboxyl or C2-C6-carboxyalkyl. It ;s part;cularly preferable for R4 to be a carboxyl group.
Base addition salts are metal, ammonium or organic ammonium salts, ;n part;cular salts of alkal; metals, alka-line earth metals, metals of the groups tIB, IIIA or ~III
of the per;odic system of the elements, ammonium salts or salts of organ;c amines. Examples of these are, in par-ticular, sodium, potass;um, calcium, magnesium, zinc, alu-minium, ammonium, trialkylammonium and tris-thydroxyethyl)-ammonium salts.
The following are examples of corrosion inhibitors of the component b):
benzthiazol-2-ylthiomalonic acid, benzthiazol-2-ylth;osuccinic ac;d, 5-methylbenzth;azol-2-ylth;osuccinic acid, 6-ethylbenzth;azol-2-ylthiosuccinic acid, 4-;sopropylbenzth;azol-2-ylth;osucc;n;c acid, 7-t-butylbenzthiazol-2-ylthiosucc;n;c acid, 5-n-hexylbenzth;azol-2-ylthiosuccinic acid, 6-(1,1,3,3-tetramethylbutyl)-benzthiazol-2-ylth;osuccinic acid, 6-cyclohexylbenzthiazol-2-ylthiosuccinic acid, 1 31 66~5 7-benzylbenzth;azol-2-ylth;osuccinic acid, b-methoxybenzthiazol-2-ylthiosuccinic acid, ~S-ethoxybenzthiazol-2-ylthiosuccinic acid, 7-ethoxybenzthiazol-Z-ylth;osuccinic acid, 5-methoxybenzthiazol-2-ylthiosuccinic acid, 4-methylthiobenzthiazol-2-ylthiosuccinic acid, 4-fluorobenzthiazol-2-ylthiosuccin;c acid, 5-chlorobenzthiazol-2-ylthiosuccinic acid, 7-bromobenzth;azol-2-ylthiosuccinic acid, 6-chlorobenzthiazol-2-ylthiosuccinic acid, 4-phenylbenzthiazol-2-ylthiosuccinic acid, 5-trifluoromethylbenzthiazol-2-ylthiosuccinic acid, S-carboxybenzthiazoi-2-ylthiosuccinic ac;d, 6-methylsulfonylbenzthiazol-2-ylthiosuccinic acid, 5-cyanobenzth;azol-2-ylthiosuccinic acid, 6-n;trobenzth;azol-2-ylth;osuccin;c ac;d, S-cyanobenzthiazol-2-ylthiosuccin;c acid, 7-hydroxybenzthiazol-2-ylthiosucc;nic acid, 6-chloro-4-methylbenzth;azol-2-ylthiosucc;nic acid, S-chloro-6-n-butylbenzthiazol-2-ylthiosuccinic acid, 4-bromo-5-n-hexylbenzthiazol-2-ylthiosuccinic acid, 5-nitro-6-n-propylbenzthiazol-2-ylthiosuccinic acid, S-bromo-6-n-propoxybenzthiazol-2-ylthiosuccinic acid, 6-aminobenzthiazol-2-ylthiosuccinic acid, 6-methylaminobenzthiazol-2-ylthiosuccinic acid, 5-dimethylaminobenzth;azol-2-ylth;osucc;n;c ac;d, 7-phenylaminobenzthiazol-2-ylthiosuccinic acid, 6-diphenylaminobenzthiazol-2-ylthiosuccinic acid, 4-benzylaminobenzthiazol-2-ylth;osuccinic acid, 4-morpholinobenzth;azol-2-ylth;osucc;nic acid, 5-carbamoylbenzthiazol-2-ylthiosuccin;c acid, 5-methylcarbamoylbenzth;azol-2-ylthiosuccin;c acid, S-diethylcarbamoylbenzthiazol-2-ylthiosucc;n;c acid, 6-phenylcarbamoylbenzth;azol-2-ylthiosuccinic acid, 5,6-dimethylbenzthiazol-2-ylth;osucc;nic acid, 4,5,6-triethylbenzth;azol-2-ylth;osuccinic acid, 4,5,6,7-tetramethylbenzth;azol-2-ylthiosucc;n;c acid, - 8 - 13~ 6~
1-(benzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(6-trifluoromethylbenzthiazol-2-ylthio)-proPane-1,2-di-carboxylic acid, 3-(6-methoxycarbonylbenzthiazol-2-ylthio)-propane-1,2-di-carboxylic acid, 3-(6-aminobenzthiazol-2-ylthio)~propane-1,2-dicarboxylic acid, 3-(5-ethylaminobenzth;azol-2-ylthio)-propane~1,2~dicarboxy-l;c ac;d, 3-(4-dibutylaminobenzthiazol-2-ylth;o)-propane-1,2-dicar-boxylic ac;d, 4-(morphol;nobenzth;azol-2-ylthio)-propane-1,2-dicarboxylic ac;d, 1-(4-phenylbenzth;azol-2-ylth;o)-propane-1,2-dicarboxylic ac;d, 1-~benzth;azol-2-ylth;o)-propane-1,3-dicarboxylic acid, 1-(6-ethylbenzth;azol-2-ylth;o)-propane-1,3-d;carboxylic acid, 2-(benzthiazol-2-ylthio)~propane-1,3-dicarboxylic acid, 2-(5-carboxybenzthiazol-2-ylthio)-propane-1,3-dicarboxylic ac;d, 3-(benzthiazol-2-ylthio)-3-phenylpropane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-3-(4-carboxyphenyl)-propane-1,2-dicarboxyl;c acid, 3-(benzthiazol-2-ylth;o)-3-(2,4-d;carboxylphenyl)-propane-1,2-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-3,3-diphenylpropane-1,2-dicarboxy-l;c ac;d, 1-(benzthiazol-2-ylthio)-butane-1,2-dicarboxyl;c acid, 1-~4-methoxy-6-hydroxybenzthiazol-2-ylthio)-butane-1,2-di-carboxylic acid, 3-(4,5-dimethyl-7-propoxybenzthiazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(benzthiazol-2-ylthio)~2-methylpropane~1,2~dicarboxylic acid~
:. -_ 9 _ 2-tbenzthiazol-2-ylthio)-butane-2,3-dicarboxyl;c acid~
1-~benzthiazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-(benzthiazol-2-ylthio)-butane-1,2,3-tricarboxylic acid, 4-(benzthiazol-2-ylthio)-butane~1,4-dicarboxylic acid, 1-(benzthiazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-hexane~1,2~dicarboxylic acid, 8-(benzthiazol-2-ylthio)-octane-1,3,5,7~tetracarboxylic acid, 1-(benzthiazol-2-ylthio)-cyclohexane~1,2-dicarboxylic acid, ~-(benzthiazol-2-ylthio)-cyclohexane~1,2-dicarboxylic ac;d, 1-(benzth;azol-2-ylthio)-propane-1,2,3-tricarboxylic acid, 1-(benzthiazol-2-ylthio)-3-chloropropane-1~2~dicarboxylic acid, 1-(benzth;azol-2-ylthio)-3-methoxypropane-1,2-dicarboxylic acid, 1-(benzthiazol-2-ylthio)-3-hydroxypropane-1,2-dicarboxylic ac;d, 1-(benzth;azol-2-ylth;o)-2-phenylsucc;nic acid, 1-(benzthiazol-2-ylthio)-2-benzylsucc;nic acid, 1-~benzthiazol-2-ylthio)-3-methylbutane-1,3-dicarboxylic acid, 3-(benzthiazol-2-ylthio)-hexane-3,4-dicarboxylic acid, 2,3-bis-~benzthiazol-2-ylthio)-butane-1,4-dicarboxylic acid, disodium benzthiazol-2-ylthiosuccinate, dlpotassium benzthiazol-2-ylthiosuccinate, calcium benzthiazol-2-ylthiosuccinate, zinc benzthiazol-2-ylthiosuccinate, cobalt benzthiazol~2~ylthiosuccinate, alumin;um benzthiazol-2-ylthiosuccinate, ammon;um benzth;azol-2-ylth;osuccinate, bis-methylammonium benzthiazol-2-ylthiosuccinate, bis-triethanolammon;um benzth;azol-2-ylthiosuccinate, b;s-octylammonium benzth;azol-2-ylth;osuccinate, bis-cyclohexylammonium benzthiazol-2-ylthiosuccinate, diethylammonium benzthiazol-2-ylthiosuccinate, tributylam~onium benzthiazol~2~ylthiosuccinate, 1 ~1 66~
d;sodium 3-(benzthiazol-2-ylthio)~propane-1,2-dicarboxylate, dipotassium 3-(benzthiazol~2~ylthio)~propane-1,2~dicarboxy~
late, calcium 3-~benzthiazol-2-ylthio)-propane-1,2-dicarboxy-late, zinc 3-(benzthia2ol-2-ylthio)-propane-l~2-dicarboxylate~
aluminium 3-(benzthiazol~2-ylthio)-propane-1,2-dicarboxy-late, ammonium 3-(benzth;azol-2-ylthio)-propane~1,2~dicarboxy-late, bis-methylammon;um 3-(benzthiazol-2-ylthio)-propane-1,2-d;-carboxylate, bis-(tr;ethanolammonium) 3-(benzth;azol-2-ylthio)-propane-1,2-dicarboxylate, benzoxazol-2-ylthiomalon;c acid, benzoxazol-2-ylth;osucc;n;c acid, 5-methylbenzoxazol-2-ylth;osùcc;nic acid, 6-ethylbenzoxazol-2-ylth;osucc;nic ac;d, 4-;sopropylbenzoxazol-2-ylth;osucc;nic acid, 7-t-butylbenzoxazol-2-ylth;osucc;n;c ac;d, 5-n-hexylbenzoxazol-2-ylth;osucc;n;c ac;d, 6-C1,1,3,3-tetramethylbutyl~-benzoxazol-2-ylthiosucc;n;c ac;d, 6-cyclohexylbenzoxazol-2-ylth;osucc;n;c ac;d, ~-benzylbenzoxazol-2-ylth;osucc;n;c ac;d, 6-methoxybenzoxazol-2-ylth;osucc;n;c acid, 7-ethoxybenzoxazol-2-ylthiosuccinic ac;d, 1 31 6~S5 6-ethoxybenzoxazol-2-ylthiosucc;nic acid, S-methoxybenzoxazol-2-ylthiosuccinic acid, S-ethoxycarbonylbenzoxazol-2-ylthiosuccinic acid, 4-methylthiobenzoxazol-2-ylthiosuccinic acid, 6-methylsulfonylbenzoxazol-2-ylthiosuccinic acid, 4-fluorobenzoxazol-2-ylthiosuccinic acid, S-chlorobenzoxazol-2-ylthiosuccinic acid, 7-bromobenzoxazol-2-ylthiosuccinic ac;d, 6-chlorobenzoxazol-2-ylthiosuccinic acid, 4-phenylbenzoxazol-2-ylth;osucc;n;c acid, 6-nitrobenzoxazol-2-ylthiosuccin;c ac;d, 5-cyanobenzoxazol-2-ylth;osuccinic acid, S-carboxybenzoxazol-2-ylthiosuccinic acid, 7-hydroxybenzoxazol-2-ylthiosuccin;c acid, 6-chloro-4-methylbenzoxazol-2-ylth;osuccinic acid, 5-chloro-6-n-butylbenzoxazol-2-ylth;osuccinic acid, 4-bromo-5-n-hexylbenzoxazol-2-ylth;osuccinic ac;d, S-nitro-6-n-propylbenzoxazol-2-ylth;osucc;n;c acid, 5-bromo-6-n-propoxybenzoxazol-2-ylth;osucc;nic ac;d, 6-am;nobenzoxazol-2-ylth;osucc;n;c ac;d, 6-methylam;nobenzoxazol-2-ylth;osucc;nic acid, S-d;methylaminobenzoxazol-2-ylthiosuccinic acid, 7-phenylam;nobenzoxazol-2-ylthiosuccinic acid, 6-diphenylaminobenzoxazol-2-ylth;osuccinic acid, 4-benzylaminobenzoxazol-2-ylthiosuccinic acid, 4-morpholinobenzoxazol-2-ylthiosuccinic acid, 5-carbamoylbenzoxazol-2-ylthiosuccinic acid, S-methylcarbamoylbenzoxazol-2-ylthiosuccinic acid, S-diethylcarbamoylbenzoxazol-2-ylthiosuccinic acid, 6-phenylcarbamoylbenzoxazol-2-ylthiosuccinic acid, 5,6-dimethylbenzoxazol-2-ylthiosuccinic acid, 4,5,6-triethylbenzoxazol-2-ylthiosuccinic acid, 4,5,6,7-te~ramethylbenzoxazol-2-ylthiosuccin;c acid, 1-(benzoxazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(4-phenylbenzoxazol-2-ylthio)-propane-1,2-dicarboxyl;c acid, 3-~benzoxazol-2-ylthio~-propane-1,2-d;carboxylic acid, 1 31 66~,5 3-(6-tr;fluoromethylbenzoxazol-2-ylthio)-propane-1-2-dicar-boxylic acid, 3-(6-methoxycarbonylbenzoxazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 3-(6-aminobenzoxazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(5-ethylaminobenzoxazol-2-ylthio)-propane-1,2-dicarboxy-lic acid, 3-(4-dibutylaminobenzoxazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 4-tmorpholinobenzoxazol-2~ylthio)~propane~1,2~dicarboxylic acid, 1-(benzoxazol-2-ylthio)-propane-1,3-dicarboxylic acid, 1-~6-ethylbenzoxazol-2-ylthio)-propane-1,3-dicarboxylic acid, 2-~benzoxazol-2-ylthio)-propane-1,3-d;carboxylic acid, 2-~5-carboxybenzoxazol-2-ylth;o)-propane-1,3-dicarboxylic acid, 3-(benzoxazol-2-ylth;o~-3-phenylpropane-1,2-d;carboxylic acid, 3-(benzoxazol-Z-ylth;o)-3-(4-carboxyphenyl~-propane-1,2-di-carboxylic ac;d, 3-(benzoxazol-2-ylthio~-3-(2,4-dicarboxyphenyl)-propane-1,2-dicarboxylic acid, 3-(benzoxazol-2-ylthio)-3,3-diphenylpropane-1,2-dicarboxy-l;c acid, 1-(benzoxazol-2-ylthio)-butane-1,2-dicarboxylic acid, 1-(4-methoxy-6-hydroxybenzoxazol-2-ylthio)-butane-1,2-di-carboxylic acid, 3-(4,5-dimethyl-7-propoxybenzoxazol-2-ylthio~-propane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio~-2-methylpropane-1,2-d;carboxylic acid, 2-(benzoxazol-2-ylthio)-butane-2,3-dicarboxylic acid, 1-(benzoxazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-~benzoxazol-2-ylthio~-butane-1,2,3-tricarboxylic acid, 4-(benzoxazol-2-ylthio)-butane-1,4-dicarbo%ylic acid, 1 31 66~,5 1-~benzoxazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benzoxazol-2-ylthio)-hexane-1,2-dicarboxylic asid, ~-(benzoxazol-2-ylthio)-octane-1,3,5,7-tetracarboxylic acid, 1-(benzoxazol-2-rlthio)-cyclohexane-1,2-dicarboxylic acid, 4-(benzoxazol-2-ylthio)-cyclohexane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio)~propane-1,2,3-tricarboxylic acid, 1-(benzoxazol-2-ylthio)~3~chloropropane-1,2-dicarboxylic acid, 1-~benzoxazol-2-ylthio)-3-methoxypropane-1,2~dicarboxylic acid, 1-(benzoxazol-2-ylthio)-3-hydroxypropane-1,2-dicarboxylic acid, 1-(benzoxazol-2-ylthio)-2-phenylsucçinic acid, 1-~benzoxazol-2-ylthio)-2-benzylsuccinic acid~
1-tbenzoxazol-2-ylth;o)-3-methylbutane-1,3-dicarboxylic acid, 3-~benzoxazol-Z~ylthio)~hexane-3,4~dicarboxyl;c acid, 2,3-bis-~benzoxazol-2-ylthio)-butane-1,4-dicarboxylic acid, disodium benzoxazol-2-ylth;osuccinate, dipotassium benzoxazol-Z-ylthiosuccinate, calcium benzoxazol-2-ylthiosuccinate, zinc benzoxazol-2-ylthiosuccinate, cobalt benzoxazol-2-ylthiosuccinate, ammonium benzoxazol-2-ylthiosuccinate, bis-methylammonium benzoxazol-2-ylthiosuccinate, bis-triethanolammonium benzoxazol-2-ylthiosuccinate, bis-octylammon;um benzoxazol-2-ylthiosuccinate, bis-cyclohexylammonium benzoxazol-2-ylthiosuccinate, diethylammoniùm benzoxazol-2-ylthiosuccinate, tributylammonium benzoxazol-2 ylthiosucc;nate, disodium 3-(benzoxazbl-2-ylthio)-propane-1,2-dicarboxylate, dipotassium 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxy-late, calcium 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxyLate, zinc 3-(benzoxazol-2-ylthio~-propane-1,2-dicarboxylate, ammon;um 3-(benzoxazol-2-ylthio)-propane-1,2-dicarboxylate, 1 31 66'',5 bis-methylammonium 3-(benzoxazol-2-ylthio)~Propane-l~2-d carboxyLate, b;s-triethanoLammonium 3-~benzoxazoL-2-yLthio)~Propane-l,Z-dicarboxylate, benzimidazol-2-ylthiomalon;c acid, benzimidazol-2-ylthiosuccinic acid, 5 (or 6)-methylbenzim;dazol-2-ylth;osuccinic acid, 6 (or 5)-ethylbenzimidazol-2-ylthiosuccin;c acid, 4 (or 7)-isopropylbenzimidazol-2-ylthiosuccinic acid, ? tor 4)-t-butylbenz;midazol-2-ylth;osucc;nic acid, S ~or 6)-hexylbenzim;dazol-2-ylth;osuccin;c acid, 6 (or S)-Ct,1,3,3-tetramethylbutyl~-benzimidazol-2-ylthio-succinic acid, 7 (or 4)-benzylbenzimidazol-2-ylthiosuccinic acid, 6 (or 5)-methoxybenzimidazol-2-ylthiosuccinic acid, 5-ethoxycarbonylbenzimidazol-2-ylthiosuccinic acid, 6 (or 5)-ethoxybenzimidazol-2-ylth;osucc;n;c ac;d, 7 ~or 4)-ethoxybenzimidazol-2-ylthiosuccinic acid, 4 (or 7)-fluorobenzimidazol-2-ylthiosuccinic acid, 5 tor 6)-chlorobenz;midazol-2-ylthiosuccinic acid, 7 (or 4)-bromobenzim;dazol-2-ylthiosuccin;c acid, 6 ~or 5)-nitrobenzimidazol-2-ylthiosuccinic acid, S ~or 6)-methylsulphonylbenz;midazol-2-ylthiosuccin;c acid~
1-(benzimidazol-2-ylthio)-2-phenylsuccinic acid, S (or 6)-chloro-4 (or 7)-methylbenzimidazol-2-ylthiosuc-cinic acid, 1 31 66~5 , 5 S (or 6)-chloro-6 tor 5)-n-butylbenzimidazol-2-ylth;osuc-cinic acid, 4 tor 7)-bromo-5 (or 6)-n-hexylbenzimidazol-2-ylthiosuc-cinic acid, S (or 6)-nitro-6 tor 5)-n-propylbenzimidazol-2-ylthiosuc-cinic acid, 5 tor 6)-bromo-6 (or 5)-n-propoxybenzimidazol-2-ylthiosuc-cinic acid, 5,6-dimethylbenzimidazol-2-ylthiosuccinic acid, 4,5,6-triethylbenzimidazol-2~ylthiosuccinic acid, 4,5,6,7-tetramethylbenzim;dazol~2~ylthiosuccinic acid, 5 (or 6)-aminobenzimidazol-2-ylthiosuccinic acid, t1- benzim;dazol-2-ylthio)-propane-1,2-dicarboxylic acid, 1-(4 (or 7)-phenylbenzim;dazol-2-ylthio)-propane-1,2-dicar-boxyl;c ac;d, 1-(benz;m;dazol-2-ylth;o)-propane-1,3-dicarboxyl;c acid, 1-(6 (or 5)-ethylth;obenzim;dazol-2-ylth;o)-propane-1,3-di-carboxyl;c ac;d, 2-(benzimidazol-2-ylthio)-propane-1,3-dicarboxylic acid, 2-t5 (or 6)-carboxybenzim;dazol-2-ylthio)-propane-1,3-di-carboxyl;c ac;d, 3-tbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(5 (or 6)-aminobenzimidazol-2-ylthio)-propane-1,2-dicar-boxyl;c acid, 3-t5 tor 6)-ethoxycarbonylbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-t5 tor 6)-trifluoromethylbenzimidazol-2-ylthio)-propane-1,2-dicarboxylic acid, 3-(4 (or 7)-dipropylaminobenzimidazol-2-ylthio)-propane-1,2-dicarboxylic ac;d, 3-(4 (or 7~-morphol;nobenz;midazol-2-ylth;o)-propane-1,2-dicarboxylic acid, 3-(5 (or 6)-carbamoylbenzimidazol-2-ylthio)-propane-1,2-di-carboxylic ac;d, 3-(4 tor 7)-cyanobenzim;dazol-2-ylthio)-propane-1,2-dicar-boxylic acid, 3-(benzim;dazol-2-ylthio)-3-phenylpropane-1,2-dicarboxylic 1 31 6G',5 - ~6 -acid, 3-(benzimidazol-2-ylthio)-3-(4-carboxyphenyl)-propane-1,2-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-3-~2,4-dicarboxyphenyl)-propane-1,2-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-3,3-diphenylpropane-1,2-dicar-boxylic acid, 1-~benzimidazol-2-ylthio)-butane-1,2-dicarboxylic acid, 1-~4 (or 7)-methoxy-6 (or 5)-hydroxybenzimidazol-2-ylthio)-butane-1,2-dicarboxylic acid, 4-(benz;midazol-2-ylthio)-butane-1,2,3-tr;carboxylic acid, 1-(4 (or 7)-methyl-7 ~or 4)-propoxybenzimidazol-2-ylthio)-propane-2,3-dicarboxylic acid, 1-(benzimidazol-2-ylth;o)-2-methylpropane-1,2-dicarboxylic acid, 2-(benzimidazol-2-ylthio)-butane-2,3-dicarboxylic acid, 1-(benz;midazol-2-ylthio)-butane-2,4-dicarboxylic acid, 4-(benz;m;dazol-2-ylth;o)-butane-1,4-dicarboxyl;c acid, 1-~benzimidazol-2-ylthio)-pentane-1,5-dicarboxylic acid, 3-(benz;midazol-2-ylth;o)-hexane-1,2-d;carboxylic acid, 8-(benzim;dazol-2-ylthio)-octane-1,3,5,7-tetracarboxylic ac;d, 1-~benzimidazol-2-ylthio)-cyclohexane-1,2-dicarboxylic ac;d, 4-(benzimidazol-2-ylthio)-cyclohexane-1,2-dicarboxylic acid, 1-~benzimidazol-2-ylthio)-propane-1,2,3-tricarboxylic acid, 1-(benzimidazol-2-ylthio)-3-chloropropane-1,2-dicarboxylic acid, 1-~benzimidazol-2-ylthio)~3-methoxypropane-1,2~dicarboxylic ac;d, 1-(benzimidazol-2-ylthio)-3-hydroxypropane-1,2-d;carboxylic acid, 1-(benzimidazol-2-ylthio)-3-methylbutane-1,3-dicarboxylic acid, 3-~benzimidazol-2-ylthio)-hexane-3,4-dicarboxylic acid, disodium benzimidazol-2-ylthiosuccinate, dipotassium benzimidazol-2-ylthiosuccinate, 1 31 66~ ~
calc~um ben2imida20l-2-ylthiosuccinate, 2~nc benzlmidazol-2-ylthiosuccinate, cobalt ben2imidazol-2-ylthiosuccinate, ammonium benz~midazol-2-ylthiosuccinate, b1s-methylammon1um benz~midazol-2-ylthiosuccinate, b1s-triethanolammonium benzim1dazol-2-ylthiosuccinate, bis-octylammonium benzim~dazol-2-ylthiosuccinate, bis-cyclohexylammon~um benzlmida20l-2-ylthiosuccinate and d;ethylammonium ben21m1dazol-2-ylthiosuccinate.
tO The compounds of the formula II which are used ln accord~nce uith the ~nventlon as corros~on 1nhlb1-tors are knoun compound ; The preparatlon of the compounds tan be effected in accordance u~th a proces~ of European Patent Applicat~on Publ.
No. 129506, by reactlng a compound of the formula III
R\t~ ~./ ~ III
R
ln uhlch A ls a leavlng group, for example Cl, Or, I or p-tosyloxy, ulth a compound ot the tormula ~R
1n ~h~ch 11 ~s hydrogen or a catlon, for example an alkall metal cat10n, ~lkallne earth metal cat~on or ammon~um cat-20 lon. Alternativelr, a compound of the formula IV
1316~ 5 I ll ~ -S-M IV
R ~ ~
can be reacted with a compound of the formula Compounds of the formula ~I in which X ;s sulfur or NH and R4 ;s carboxyl can aLso be prepared by reacting IV, ;n wh;ch M ;s hydrogen and X is S or NH, with an a, ~-un-saturated ac;d o~ the formula l 2 =c~
R COOH
in accordance with a process which ;s the subject of Europ. Patent Application Publ. No. 126030.
The component a) can be any des;red film-former, such as those wh;ch are known as binders for aqueous coating compGs;tions e.g. dispersion paints, emulsion paints or electrodepositable paints. The aqueous binder used as component a) may be one or more water-soluble or water-dispersible synthetic polymer. Examples of such polymers are alkyd, polyester, acrylic, polyurethane, epoxide, phenoplast or aminoplast resins and mixtures of these resins,and homo- or copolymers of vinyl ethers, vinyl esters, styr-ene, vinylidene chloride and v;nyl chloride.
The water-borne binder may be optionally crosslinked with aminoplast resins, phenoplast resins, blocked isocyanates, epoxy resins, Mannic h bases of phenols or activated carboxylic esters.
: -1 3 1 66~,5 There are several methods available for rendering these binders suitable for use in water-borne paints. These methods, which are well known to those skilled in the coatings art, include the incorporation of basic or acidic functional groups which are then neutralised prior to d;lution with water~
In addition to the components a) and b), the coat-ing composition can also contain further components, for example pigments, dyes, extenders and other additives such as are customary for water-borne coating compositions. The pigments can be organic, inorganic or metallic pigments, for example titanium dioxide, iron oxide, aluminium bronze, phthalocya-nine blue etc. It is also possible to use concomitantly anti-corrosion pigments, for example pigments containing phosphates or borates, metal pigments and metal oxide pig-ments (see Farbe und Lack 88 (1982), 183) or the ~igments described in European Patent A 54,267. Examples of exten-ders hhich can be used concomitantl~ are talc, chalk, alu-mina, baryte, mica or silica. ~xamples of 'urtner addi-tives are flow control auxiliaries, dispersing agents, th;xotropic agents, adhesion promoters, an.ioxidants, light stabilisers or curing catalysts.
Particular importance attaches to the addi;ion of basic extenders or pigments. In certain binder systems, for example in acrylic and alkyd resins, these produce a synergistic effect on the inhibition of corrosion.
Examples of such basic extenders or pigments are calcium carbonate, magnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, aluminium oxide, aluminium phosphate or mixtures thereof. Examples of pigments are those based on aminoanthraquinone.
The corrosion inhibitors according to the invention can also first be applied to such basic extenders or pig-ments, for example by chemisorption from an aqueous solu-tion, and the preparations thus obtained can be added to the coating composition.
1 31 66~5 In a further preferred embodiment of the invention the corrosic,n inh;bitors are used together ~ith basic ion exchangers or an ion exchanger of this type is first treated with a solution of the inhibitor, and this prepara-tion is then added to the coat;ng compos;tion. Examples of basic ion exchangers are all typical anion exchangers, such as those available commercially, for example under the names Dowex R 1 or 11 or Amberlite R IRA.
Finally, the corrosion inhibitor can also be app-lied to a neutral carrier. Suitable carriers are, in par-ticular, pulverulent extenders or pigments. This technique is described in greater detail in German Offenlegungs-schrift 3,122,907.
In addition to the component b), the coating composition can also contain another organic, metal-organic or inorganic corrosion inhibitor, for exam?le salts of nitro;sophthalic acid, tannin, phosphoric esters, technical amines, substituted benztriazoles or subs~ituted phenols, such as are described in German Offenlegungsschrift 3,146,~65~
The coating compositions according to the invention are preferably used as a primer on metallic substrates, in particular on iron, steel, copper and aluminium. Here they can function as so-called conversion coa;ings, in that chemical reactions take place at the interface ~etween the metal dn the coating. The coating compositions may also find application ;n can coating processes. The application of the coatings can be effected by the customary methods, such as spraying, brushing, roller-coating or dipping.
One preferred method is electrodeposition which may be either anodic or cathodic, but is preferably cathodic.
1 3 1 6 6 ~
Depending on whether the film-former is a resin which dries phys;cally or can be cured by heat or radiation, t~e cur;ng of the coatings is carried out at room temperature, by stoving or by irradiation.
The corrosion inhibitors can be added to the coat-ing composition during the preparation of the latter, for example during the distribution of the pig~ent by grinding or the ;nhibitors are dissolved beforehand in a solvent and the solution is stirred into the coating composition. The innibitor is used in an amount of û.1 - 2û,. by ~eight, pre-ferably û.5 - 5,'. by weight, based on the solids content of the ~o~tinq composition.
Example_ A water-based maintenance primer is prepared by mixing the follow;ng components (A) and (B) ~A) Pigment Paste 14.6 9 TiO2-Pigment (Ti-Pure ~ R-96û, Du Pont de Nemours Co) 1.4 9 35 % aqueous solution of an dispersing agent (Dispersing Agent QR 681 M, Rohm & Haas) 0.2 g pigment wetting agent (Triton ~ CF 10, Rohm & Haas) 4.7 9 dist. water 0.2 9 antifoaming agent (Colloids 643, Colloids Inc.) 1.2 9 zinc oxide 5.1 9 micronized CaC03 (Millicarb ~ , Pluss-Staufer) 27.4 9 1 31 6~5 ~B) Binder Dispers;on 64.4 9 43 % aqueous dispersion of an acrylic resin tPrimal ~ MV 23, Rohm & Haas) 1.0 g 2-butoxyethoxy-ethanol 2.7 9 ethylene glycol 0.2 9 mildewcide agent CSkane ~ M-8, Rohm & Haas) 0.4 9 antifoaming agent (Colloids 643, Colloids Inc.) 0.2 9 thickener (Primal ~ ICS-1, Rohm & Haas) 1.1 9 rheology modifier (Primal ~ RM-8, Rohm & Haas) 2.6 9 dist. water 72.6 9 The mixed primer has a solid content of 48 %. To this dispersion are added the corrosion inhibitors indicated in the follow;ng table.
The primer is applied to phosphatised iron sheets in a thickness of 100~um. The samples are baked at 130C for 20 m;nutes and are afterwards tested by a salt spray test according to ASTM method B-117 for a duration of 600 hours.
The condition of the coating is assessed at the cross-cut and on 'he whole surface according to DIN methods 53 209 and 53 210.
The coating is removed by treatment with concentrated NaOH
solution and the corrosion of the metal is assessed according to DIN method 53 167. In both cases the assessment is made on the basis of a 6-stage scale.
The sum of the assessment of coating and metal is the corrosion protection ~alue ~CP).
i. , I
1 3 1 6 6 ~ ' *) Assessment Assessment Corrosion Inhibitor Amount of coating of metal CP
-none - 3.6 3.9 7.5 Benzthiazol-2-ylthio-succinic acid-zinc salt 2 % 3.7 4.3 8.0 -NH4 salt 2 % 4.1 4.3 8.4 3 % 4.3 5.2 9.5 3-~Benzthiazol-2-ylthio)-propane-1,2-dicarboxylic ac;d-NH4 salt 5 % 4.4 4.5 8.9 ) related to the solid coating
Claims (23)
1. An aqueous corrosion-inhibiting coating composition containing a) an aqueous film-forming binder and b) as the corrosion inhibitor, an effective amount of an aliphatic or cycloaliphatic di-, tri- or tetra-carboxylic acid which is substituted in its aliphatic or cycloaliphatic radical by at least one group of the formula I
I
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino group, and also base addition salts of these compounds, provided that these compounds do not contain an amide, imide or nitrile group.
I
in which X is oxygen, sulfur or NH and each R independently of the others is hydrogen, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, halogen, -NO2, -COOH, -COOalkyl, -OH or a primary, secondary or tertiary amino group, and also base addition salts of these compounds, provided that these compounds do not contain an amide, imide or nitrile group.
2. A coating composition according to claim 1, containing a corrosion inhibitor containing a group of the formula I in which X
is sulfur.
-24a- 21489-6829
is sulfur.
-24a- 21489-6829
3. A coating composition according to claim 1, containing a corrosion inhibitor containing a group of the formula I in which one of the substituents R is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or an amino group and the other three Rs are hydrogen.
4. A coating composition according to claim 1, containing a corrosion inhibitor containing a group of the formula I in which each R is hydrogen.
5. A coating composition according to claim 1, in which the component b) is an aliphatic or cycloaliphatic dicarboxylic acid or a salt thereof.
6. A coating composition according to Claim 1, in which the component b) contains a group of the formula I which is in the beta-position relative to a carboxyl group.
7. A coating composition according to Claim 1, containing, as the component b), a compound of the formula II
II
in which X and R are as defined in Claim 1, n is zero or 1 and R1, R2, R3 and R4 independently of one another are hyd-rogen, alkyl, hydroxyalkyl, halogenoalkyl, alkoxyalkyl, carboxyalkyl, carboxyl or phenyl or phenylalkyl which is unsubstituted or monosubstituted or disubstituted, or R1 and R2 or R1 and R3 together are linear alkylene which can be substituted by 1 or 2 -COOH groups, or R1 and R2 together are a direct bond, at least two of the substituents R1, R2, R3 and R4 being a carboxyl or carboxyalkyl group, and also base addition salts of these compounds.
II
in which X and R are as defined in Claim 1, n is zero or 1 and R1, R2, R3 and R4 independently of one another are hyd-rogen, alkyl, hydroxyalkyl, halogenoalkyl, alkoxyalkyl, carboxyalkyl, carboxyl or phenyl or phenylalkyl which is unsubstituted or monosubstituted or disubstituted, or R1 and R2 or R1 and R3 together are linear alkylene which can be substituted by 1 or 2 -COOH groups, or R1 and R2 together are a direct bond, at least two of the substituents R1, R2, R3 and R4 being a carboxyl or carboxyalkyl group, and also base addition salts of these compounds.
8. A coating composition according to Claim 7, wherein R1, R2, R3 and R4 are hydrogen, C1-C18-alkyl, C2-C12-car-boxyalkyl, carboxyl, phenyl or benzyl, or R1 and R2 together are trimethylene or tetramethylene which can be substituted by C1-C4-alkyl or by carboxyl groups.
9. A coating composition according to Claim 7, wherein R1, R , R and R4 in formula II independently of one another are hydrogen, C1-C4-alkyl, carboxyl or C2-C6-carboxyalkyl.
10. A coating composition according to Claim 1, in which the component b) is a compound of the formula or
11. A coating composition according to Claim 1, in which the component b) is present as the salt of an alkali metal or alkaline earth metal or a metal of group IIB, IIIA or VIII of the periodic system of the elements, as an ammonium salt or as the salt of an organic amine.
12. A coating composition according to Claim 11, in which the component b) is present as a sodium, potassium, ammonium, calcium, magnesium, zinc or aluminium salt or as the salt of a primary, secondary or tertiary amine.
13. A coating composition according to Claim 1 wherein the binder is one or more water-soluble or water-dispersible synthetic polymer.
14. A coating composition according to Claim 13 wherein the polymer is an alkyd, polyester, acrylic, polyurethane, epoxide, phenoplast or aminoplast resin or homo- or copolymer of a vinyl ether, a vinyl ester, styrene, vinylidene chloride or vinyl chloride.
15. A coating composition according to Claim 1 containing, in addition to components a) and b), a pigment, a dye, an extender or other additives customary for coating compositions.
16. A coating composition according to Claim 15, containing a basic extender or a basic pigment.
17. A coating composition according to Claim 15, containing a basic ion exchanger.
18. A coating composition according to Claim 1, containing, besides the corrosion inhibitor b), one or more further corrosion inhibitors which can be organic, metal-organic or inorganic compounds.
19. A coating composition according to Claim 1, containing 0.1 to 20 % by weight of the component b), based on the solids content of the coating composition.
20. A coating composition according to Claim 1, containing 0.5 to 5 % by weight of the component b).
21. The use of a coating composition of Claim 1 as a primer *
on metallic substrates.
on metallic substrates.
22. Use according to Claim 21 as a primer on substrates composed of iron, steel, copper or aluminium.
23. Use according to Claim 21 as an electrocoating paint for cathodic electrodeposition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8428677 | 1984-11-13 | ||
| GB848428677A GB8428677D0 (en) | 1984-11-13 | 1984-11-13 | Corrosion-inhibiting aqueous coating compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1316685C true CA1316685C (en) | 1993-04-27 |
Family
ID=10569677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000494944A Expired - Fee Related CA1316685C (en) | 1984-11-13 | 1985-11-08 | Corrosion-inhibiting aqueous coating compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0183647B1 (en) |
| JP (1) | JPS61120870A (en) |
| CA (1) | CA1316685C (en) |
| DE (1) | DE3568282D1 (en) |
| GB (1) | GB8428677D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11149202B1 (en) | 2016-12-13 | 2021-10-19 | Ecolab Usa Inc. | Tetracarboxylic acid combinations for corrosion inhibition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818777A (en) * | 1986-08-27 | 1989-04-04 | Ciba-Geigy Corporation | Phenolic corrosion inhibitors for coating materials |
| US5198482A (en) * | 1989-12-14 | 1993-03-30 | Ciba-Geigy Corporation | Corrosion-inhibiting coating compositions |
| US20120024703A1 (en) * | 2010-07-28 | 2012-02-02 | Ppg Industries Ohio, Inc. | Compositions useful for electrocoating metal substrates and electrodeposition processes using the coatings |
| JP6389883B2 (en) * | 2013-10-23 | 2018-09-12 | オートノミック マテリアルズ、インコーポレイテッド | Self-healing agent formulations containing liquid corrosion inhibitors |
| CN117567892A (en) * | 2024-01-16 | 2024-02-20 | 东北大学 | Magnesium alloy anticorrosive paint and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH458048A (en) * | 1965-08-17 | 1968-06-15 | Sandoz Ag | Process for the production of optically brightened paper |
| US4329381A (en) * | 1978-02-23 | 1982-05-11 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Method for providing corrosion resistance to metal objects |
| US4235838A (en) * | 1978-08-09 | 1980-11-25 | Petrolite Corporation | Use of benzazoles as corrosion inhibitors |
| GB8313320D0 (en) * | 1983-05-14 | 1983-06-22 | Ciba Geigy Ag | Coating compositions |
| DE3341633A1 (en) * | 1983-11-17 | 1985-05-30 | Sanshin Kagaku Kogyo Co., Ltd., Yanai, Yamaguchi | Rust-inhibiting substance |
| GB8412063D0 (en) * | 1984-05-11 | 1984-06-20 | Ciba Geigy Ag | Compositions containing heterocyclic corrosion inhibitors |
| GB8412064D0 (en) * | 1984-05-11 | 1984-06-20 | Ciba Geigy Ag | Compositions containing heterocyclic corrosion inhibitors |
-
1984
- 1984-11-13 GB GB848428677A patent/GB8428677D0/en active Pending
-
1985
- 1985-11-07 EP EP19850810522 patent/EP0183647B1/en not_active Expired
- 1985-11-07 DE DE8585810522T patent/DE3568282D1/en not_active Expired
- 1985-11-08 CA CA000494944A patent/CA1316685C/en not_active Expired - Fee Related
- 1985-11-13 JP JP25297085A patent/JPS61120870A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11149202B1 (en) | 2016-12-13 | 2021-10-19 | Ecolab Usa Inc. | Tetracarboxylic acid combinations for corrosion inhibition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0183647B1 (en) | 1989-02-15 |
| DE3568282D1 (en) | 1989-03-23 |
| JPS61120870A (en) | 1986-06-07 |
| GB8428677D0 (en) | 1984-12-19 |
| EP0183647A1 (en) | 1986-06-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |