DK171533B1 - Anticorrosive coating material - Google Patents

Description

BACKGROUND OF THE INVENTION.

The present invention relates to a superior anti-corrosive coating material for metals. The material contains a chelable polyol resin, a hardener having 5 isocyanate group (s) and a bituminous material and / or its substitute.

A coating material containing polyol resin is known as an anticorrosive coating material for metal. However, in order to obtain and maintain good anti-corrosive properties 10 using this material, it is necessary to remove the rust and perform adequate treatment of the metal surface prior to coating application up to the quality St (or Sa) 2.5 of Swedish Standard SIS 05 59 00. the metal surface treated inadequately has 15 poorer adhesion and poorer anti-corrosion properties.

It was desirable to obtain a coating material with good adhesion and good anti-corrosion properties even when coating a poorly treated metal surface or even a rusty surface such as grade Sa 1 to Sa 1.5 in Swedish Standard SIS 05 59 00.

BRIEF DESCRIPTION OF THE INVENTION.

Accordingly, it is an object of the invention to provide a coating material which exhibits good adhesion and good anti-corrosion properties even when coating a poorly treated metal surface or even a rusty surface with SIS Sa 1 to 1.5. The present coating material is characterized in that it comprises 30 (A) A polyol resin obtained by reacting a prepolymer of an epoxy resin (A1) and a phosphorus compound (A-2) having at least one P-OH group selected from the group consisting of phosphorus acids, their esters, their salts and mixtures thereof, and one or more compounds 35 (A-3) with one or more amino groups reactive with epoxy groups, a compound having more than one isocyanate group or groups which change to isocyanate groups under the curing conditions, and (C) a bitominous material and / or its substitute.

The prepolymer is obtained by reaction under heating of the epoxy resin (Al) and the phosphorus-containing acid, esters thereof with at least one hydroxy group or salts thereof (A-2), optionally in the presence of a solvent in such a ratio that epoxide groups remain in the prepolymer.

Although the reaction temperature is not limited, it is less than the degradation temperature of the epoxy resin and is large enough to complete the reaction within a reasonable period of time. Generally, the reaction proceeds at 50-130 ° C.

DETAILED DESCRIPTION OF THE INVENTION.

The epoxy resins (A-1) which can be used in the reaction include e.g. an epoxy compound containing, on average, more than one 1,2-epoxy group (preferably an epoxy compound containing, on average, 2 or more groups) epoxidized polyunsaturated compounds and other well-known epoxy compound compounds containing adjacent epoxy groups.

The epoxy resin (A-1) includes e.g. epoxy compounds (A-1-1) containing on average more than one optionally substituted glycidyl ether group of the general formula 30 z

CH- - C - CH- - O

'V' (wherein Z is a hydrogen atom, a methyl or ethyl group) per molecule; epoxy compounds (A2-1-2) containing, on average, more than one optionally sub * -stituted glycidyl ester group of the general formula (wherein Z is CH2 - C - CH0 - O - CO - X / 2,5). is one hydrogen atom, one methyl or ethyl group) per molecule; and epoxy compounds (A-1-3) containing, on average, more than one optionally N-substituted glycidyl group of the general formula

Z

10 CHL - C - CH_ - N

V

(wherein Z is a hydrogen atom, a methyl or ethyl group) per molecule.

The epoxy compounds (A-1-1), which contain on average more than one optionally substituted glycidyl ether group per molecule, can be prepared by glycidyl etherifying hydroxy compounds such as phenolic hydroxyl compounds or alcoholic hydroxyl compounds.

Examples of preferred epoxy compounds (A-1-1) include e.g. polyglycidyl ethers (Al-1-1) of polyhydric phenols with one or more aromatic cores, polyglycidyl ethers (Al-1-2) of alcoholic polyhydroxyl compounds derived by addition of polyhydric phenols with one or more aromatic cores with alkylene oxides of 2-4 carbon atoms, and polyglycidyl ethers (Al-1-3) of alcoholic polyhydroxyl compounds having one or more alicyclic rings.

The polyhydric phenol polyglycidyl ethers (A-1-1-1) include e.g. epoxide compounds containing as the main reaction product (1) polyglucidyl ethers obtained by reacting polyhydric phenols (D) with at least one aromatic core with epihalohydrins (e) in the presence of basic catalysts or basic compounds such as sodium hydroxide, (2) epoxide compounds, is obtained by reacting polyhalohydrin ethers (obtained 4 reaction of polyhydric phenols (D) with at least one aromatic core with epihalohydrins (e) in the presence of catalytic amounts of acid catalysts such as boron trifluoride) with basic compounds such as sodium hydroxide and 5 ( 3) epoxide compounds obtained by reacting polyhalohydrin ethers (obtained by reaction of polyhydric phenols (D) with at least one aromatic core with epihalohydrins (e) in the presence of catalytic amounts of basic catalysts such as triethylamine) with basic compounds such as sodium hydroxide.

Such polyoxyalkylated polyhydric phenol-polyglycidyl ethers (A-1-1-2) include, e.g. epoxide compounds containing as the main reaction product polyglycidyl ethers obtained by reacting 15 polyhalohydrin ethers (obtained by reaction of polyoxyalkylated polyhydric phenols (E) obtained by the addition of polyhydric phenols with at least one aromatic core with alkylene oxides having 2-4 carbon atoms with epihalohydrins) in the presence of a catalytic amount of acid catalyst such as boron trifluoride) with basic compounds such as sodium hydroxide.

The polyvalent phenols with at least one aromatic core (D) include polyvalent single-core phenols with an aromatic core (D-1), and polyvalent poly-core phenols with at least two aromatic cores (D-2).

Examples of polyvalent single-core phenols (D-1) include e.g. resorcinol, hydroquinone, pyrocatechol, phlorocgiycinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxy-naphthalene, 2,6-dihydroxynaphthalene and the like.

Examples of polyhydric polynuclear phenols (D-2) include divalent polynuclear phenols of the following general formula (1) ΓΤ1 · “P1 1 2 ′ 35 HO - Ar - [R1] 1 - Ar - OH U> Wherein: Ar is an aromatic divalent hydrocarbon group or a radical such as naphthylene and phenylene, with phenylene being preferred; Y 1 and Y 1 which may be the same or different are alkyl groups such as methyl, n-propyl, n-5 butyl; n-hexyl, n-octyl and the like, preferably alkyl groups having a maximum of 4 carbon atoms, or halogen atoms ie chlorine, bromine, iodine or fluorine, or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy and the like, preferably a alkoxy group having a maximum of 4 carbon atoms (it is noted that when substituents other than hydroxyl groups are present on one or both of the aromatic divalent hydrocarbon groups, then these substituents may be the same or different), an integer having the value 0 or 1, m and z are integers 15 from 0 ti 1 is a maximum value corresponding to the number of hydrogen atoms on the aromatic ring (Ar); which may be replaced by substituents and may have the same or different values and R 1 is a divalent group or radical such as e.g.

-C-,

II

o -O-, -S-, -SO-, or -SO2-, or a divalent hydrocarbon group such as e.g. an alkylene group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexymethylene, octamethylene, nonamethylene, decamethylene, and the like, an alkylidene group such as ethylidene, propylidene, isopropylidene, isobutylidene, amylidene, , 1-phenylethylidene and the like, or a cycloaliphatic group such as 1,4-cyclohexylene, 1,3-cyclohexylene, cyclohexylidene and the like, or halogenated alkylidene, alkylene or cycloaliphatic groups, alkoxy or aryloxy substituted alkylidene, alkylene or cycloaliphatic groups such as methoxy-methylene, ethoxymethylene, ethoxyethylene, 2-ethoxy-trimethylene, 3-ethoxypentamethylene, 1,4- (2-methoxy-cyclohexane), phenoxyethylene, 2-phenoxytrimethylene, 1,3- (2) -phenoxycyclohexane) and the like, aralkylene groups such as phenylethylene, 2-phenyltrimethylene, 1-phenyl-pentamethylene, 2-phenyldecamethylene and the like, aromatic groups such as phenylene, napthylene and the like, halogenated aroma groups such as 1,4 - ((2-chlorophenylene), 1,4- (2-bromophenylene), 1,4- (2-fluorophenylene) and the like, alkoxy or aryloxy-substituted aromatic groups such as 1,4- (2-methoxyphenylene), 1,4- (2-ethoxyphenylene), 1,4- (2-n-propoxyphenylene), 1,4- (2-phenoxyphenylene) and the like, alkyl substituted aromatic groups such as 1,4- (2-methylphenylene), 1,4- (2-ethylphenylene), 1,4- (2-n-propylphenylene), 1,4- (2-n-butylphenylene), 1, 4- (2-n-dodecylphenylene) and the like, or R1 is a ring fused to one of the Ar groups, such as e.g. these are cases in connection with the formula

// - a- OH

Or is a polyalkoxy group such as polyethoxy, polypropoxy, polythioethoxy, polybutoxy, polyphenyl1-ethoxy, or R1 is a group having a silicon atom such as e.g. polydimethylsiloxy, polydiphenylsiloxy, polymethylphenylsiloxy and the like, or R4 is two or more alkylene or alkylidene groups separated by an aromatic ring, a tertiary anino group, an ether bond, a carbonyl group or separated by a bond containing sulfur such as sulfur, sulfoxide and 35 similar.

Particularly preferred as the divalent polynuclear phenols are compounds of the general formula (i) wherein Y 'and i are as previously defined, m and z have values are from 0 to 4 inclusive, and R 2 is an alkylene or alkylidene group, preferably having 1-3 carbon atoms, or R 1 is a phenylene group of formula 10- or is a saturated group of formula -o-r '*. 0 '^ CH3 CH3-C- CH3 20

Examples of particular divalent phenols include, among others, the bis (hydroxyphenyl) alkanes such as 2,2-bis (p-hydroxyphenyl) propane, commonly called bisphenol-A, 2,41-dihydroxy-diphenylmethane, 25 bis- (2- hydroxyphenyl) methane, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1.2 -bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-2-chlorophenyl) -ethane, 1,1-bis- (3,5-dimethyl-1-4-hydroxyphenyl) ethane, 1 , 3-Bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) -propane, 2,2, -bis- (3-isopropyl-4-hydroxyphenyl) ) -propane, 2,2-bis- (2-isopropyl-4-hydroxy-phenyl) propane, 2,2, -bis- (4-hydroxynaphthyl) -propane, 2,2-bis- (4-hydroxyphenyl) -pentane, 3,3, -bis- (4-hydroxy-phenyl) -pentane, 3,3, -bis- (4-hydroxyphenyl) -heptane, bis- (4-hydroxyphenyl) -phenyliftethane, bis- (4-hydroxyphenyl) -cyclohexyl-methane, 1,2-bis- (4-hydroxyphenyl) -1,2-bis-phenyl) propane, 2,2-bis- (4-hydroxyphenyl) -1-phenyl-propane and similar, dihydroxybiphenyls such as 4,4-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,4-dihydroxybiphenyl and the like, di (hydroxyphenyl) sulfones such as 5 bis (4-hydroxyphenyl) sulfone, 2.4 '-dihydroxydiphenylsulfone, 5'-chloro-2,4, -di-hydroxydiphenylsulfone, 5'-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenylsulfone and the like, di (hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether, 4,3'-, 4,2'-, 2,2'-, 2,3'-dihydroxydiphenyl ether, 4,4'-dihydrpxy-2,6 -dimethyldiphenyl ether, bis (4-hydroxy-3-iso-butylphenyl) ether, bis (4-hydroxy-3-isopropyl-phenyl) ether, bis- (4-hydroxy-3-chlorophenyl) ether, bis - (4-hydroxy-3-fluorophenyl) ether, bis (4-hydroxy-3-bromo-phenyl) ether, bis- (4-hydroxynaphthyl) ether, bis- (4-hydroxy-3-chloro naphthyl) ) ether, bis (2-hydroxybiphenyl) ether, 4,4'-dihydroxy-2,6-dimethoxy-diphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, and the like, are also suitable. 1,1-bis- (4-hydroxyphenyl) -2-phenylethane, 1,3,3'-trimethyl-1- (4-hydroxyphenyl) ) -6-hydroxyindane, 2,4-bis- (p-hydroxyphenyl) -4-methylpentane and the like.

Other examples of divalent tokenized phenols are biphenols such as 4,4'-dihydroxybiphenyl, 3-methyl-4,4'-dihydroxybiphenyl, octachloro-4,4'-dihydroxy-biphenyl and the like.

Furthermore, other divalent polynuclear phenols of the general formula are preferred

HO 1 * 2 R2 OH

wherein R 3 is a methyl or ethyl group, eg an allylidene or other alkylene group having from 1-9 carbon atoms and 35 p ranges from 0 to 4. Examples of divalent polynuclear phenols of formula (1-2) include 1,4-bis <- (4-hydroxybenzyl) -benzene, 1,4-bis- (4-hydroxybenzyl) tetra-1-methylbenzene, 1,4-bis (4-hydroxybenzyl) -tetraethyl-benzene, 1,4-bis bis (p-hydroxycumyl) benzene, 1,3-bis (p-hydroxycumyl) benzene and the like.

Other examples of polyhydric polynuclear 5 phenols (D-2) include, for example, condensation products of phenols with carbonyl compounds (e.g. condensation products of phenolic resin, condensation products of phenols with acroleins, condensation products of phenols with glyoxal, condensation products of phenols 10 with pentanediol , condensation products of resorcinols with acetone, and condensation products of xylenes and phenols with formalin) and condensation products of phenols with polychloromethylated aromatic compounds (eg condensation products of phenols with bischloromethylxylene).

The polyoxyalkylated polyhydric phenols (E) are compounds obtained by reacting the aforementioned polyhydric phenols (D) with at least one aromatic core with an alkylene oxide in the presence of such catalysts which will promote the reaction of the OH group with the epoxy group and having atomic groups having -ROH (wherein R is an alkylene group derived from an alkylene oxide) and / or - (RO) nH (wherein R is an alkylene group derived from an alkylene oxide, a polyoxyalkylene chain may contain different alkylene groups and n is an integer of two or more indicating the number of polymerized oxyalkylene groups) bound to the phenol residue with an ether bond.

In this case, the ratio of alkylene oxide to the polyhydric phenol (D) is greater than 1: 1 (mol: mol).

However, the ratio of the alkylene oxide to the OH group of the polyhydric phenol (D) is preferably 1 to 1:10 or more preferably 1 to 3: 1 by equivalents.

The alkylene oxides include e.g. ethylene oxide, propylene oxide and butylene oxide, and particularly preferred are those which will produce branched chains in the case of preparation of ether bonds by their reaction with polyhydric phenols. Preferred examples thereof include propylene oxide and 2,3-butylene oxide, and a particularly preferred example thereof is propylene oxide.

Particularly preferred among polyoxyalkylated polyhydric phenols (E) are those of the following general formula (Y ') m (Yx) 2

H (OR) n ^ O -— -R-Q-O (RO) n ^ H

Wherein Y 1, m 2 and have the same meaning as given by the general formula (1-1), R is an alkylene group of 2-4 carbon atoms and n 1 and n 2 are from 1-3.

In addition, among the polyoxyalkylated polyhydric phenols (E), those of the following general formula (R3> p H (OR) 'O ° {R0> n2a ni are preferred in which R for the general formulas (1-1) and (1-2), R is an alkylene group having 2-4 carbon atoms and R 2 and n 2 are from 1-3.

Furthermore, as epoxy compounds (A-1-2) having an average of more than one optionally substituted glycidyl ester group in the molecule, polyglycidyl esters of aliphatic polycarboxylic or aromatic polycarboxylic acids can be used. For example. For example, an epoxy resin such as that obtained by polymerizing glycidyl methacrylate synthesized from an epihalohydrin (s) indicated by the general formula (4) 35 and methacrylic acid mentioned below may be used.

Furthermore, as examples of epoxy compounds (Al-3) having an average of more than one optionally substituted glycidyl group in the molecule, epoxy resins obtained from aromatic amines (e.g. aniline or aniline) may be mentioned. with alkyl substituent (s) in the nucleus) and epihalohydrins (e) indicated by the general formula (4) mentioned below and epoxy resins obtained from pre-condensers of aromatic amines and aldehydes (e.g., aniline-formaldehyde-precondensates or aniline resins). phenol-formaldehyde precondensates) and epihalohydrins (e).

Said polyhydric alicyclic alcohol polyglycidyl ethers (A-1-3) include, e.g. epoxide compounds containing as the main reaction product polyglycidyl ethers obtained by reaction of polyhydric alcohols (F) with at least one alicyclic ring 15 with epihalohydrins (e) in the presence of basic catalysts or basic compounds such as sodium hydroxide, the epoxide compounds obtained by reaction of polyhalohydrin ether, obtained by reaction of polyhydric alcohols (F) with at least one alicyclic ring with epihalohydrins (e) in the presence of catalytic amounts of acid catalysts such as boron trifluoride, with basic compounds such as sodium hydroxide, and epoxide compounds, obtained by reacting polyhalohydrin ethers obtained by reaction of polyhydric alcohols (F) with at least one alicyclic ring with epihalohydrins (e) in the presence of catalytic amounts of basic catalysts such as triethylamine, with basic compounds such as sodium hydroxide.

Similarly, such polyglycidyl ethers (A-1-1-3) include e.g. epoxide compounds containing as the main reaction product polyglycidyl ethers obtained by reacting polyhalohydrin ethers obtained by reaction of polyhydroxyl compounds (G), derived by addition of polyhydric alcohols (F) with at least one alicyclic ring containing 2-4 carbonate oxides with epihalohydrins (e) in the presence of catalytic amounts of acid catalysts such as boron trifluoride, with basic compounds such as sodium hydroxide.

Preferred examples of polyglycidyl ethers (Al-1-3) are polyglycidyl ethers from polyhydric alcohols having at least one alicyclic ring, and polyglycidyl ethers obtained by an addition reaction of polyhydric alcohols with at least one alicyclic ring with an alkylene oxide of 2- 4 carbon atoms.

Said polyglycidyl ethers (A-1-1-3) can be prepared by hydrogenation of aromatic rings in epoxy resins for alicyclic rings. The epoxide resin is obtained from polyhydric phenols with at least one aromatic ring such as polyglycidyl ethers of polyhydric phenols. Useful catalysts for the hydrogenation are e.g. rhodium or ruthenium 15 applied to a carrier. For example. those disclosed in Japanese Patent Publication No. 42-7788 (7788/1967).

Said polyhydric alcohols having at least one alicyclic ring (F) include polyhydric single-core alcohols with an alicyclic ring (F-1) and polyhydric polynuclear alcohols having at least 2 alicyclic rings (F-2).

It is preferred that polyhydric single-core alcohols (F1) include divalent single-core alcohols of the following formula (2): HO- (R4) fA- (R5) g-OH (2) wherein A is a divalent cyclohexane ring which may be substituted by alkyl groups , such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl and the like, preferably alkyl groups having a maximum of 4 carbon atoms, or halogen atoms, i.e. chlorine, bromine, iodine or fluorine, or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy and the like, preferably an alkoxy group having a maximum of 4 carbon atoms for the flammability properties optionally substituted by halogen atoms.

And R 1, which may be the same or different, are alkylene groups such as methylene, n-propylene, n-butylene, n-hexylene, n-octylene and the like, preferably alkylene groups having a maximum on 6 carbon carbons. f and g, 5 which may be the same or different, are 0 or 1, preferably 0.

Examples of divalent monocyclic alcohols with a cyclohexane ring are e.g. optionally substituted cyclohexanediols such as 1,4-cyclohexanediol, 2-methyl-ΙΟ 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, 1,3-cyclohexanediol and the like, optionally substituted dihydroxyalkyl-cyclohexane such as 1,4-dihydroxymethylcyclohexane , 1,4-dihydroxyethyl-cyclohexane, 1,3-dihydroxyethylcyclohexane, 1,4-dihydroxy-propylcyclohexane, 1,4-dihydroxybutylcyclohexane and the like.

Additional polyhydric single-core alcohols with an alicyclic ring other than a cyclohexane ring may be optionally substituted cycloalkyl polyols such as 1,3-cyclopentanediol, 1,4-cycloheptanediol, 1,3-20 cycloheptanediol, 1,5-perhydronaphthalenediol, 1,3-dihydroxy-2 , 2,4,4-tetramethylcyclobutane, 2,6-dihydroxydecahydronaphthalene, 2,7-dihydroxydecahydronaphthalene, 1,5-dihydroxydecahydronaphthalene and the like, and optionally substituted polyhydroxyalkylcycloalkanes such as 1,3-dihydroxymethylcycloalkylcycloalkane methylcycloheptane, 2,6-bis (hydroxymethyl) decahydronaphthalene, 2,7-bis (hydroxymethyl) decahydronaphthalene, 1,5- (hydroxymethyl) decahydronaphthalene, 1,4-bis (hydroxymethyl) decahydronaphthalene, 1.4 -bis (hydromethyl) -bicyclo [2,2,2] -octane and dimethyloltricyclodecane.

Particularly preferred as the polyhydric monocyclic alcohol is 1,4-dihydroxymethylcyclohexane for the sake of economy.

Additional polyhydric polycyclic alcohols (f-2) include e.g. polyhydric polycyclic alcohols of the following general formula (3): B1 HO- (R2) f- (A1) k - [(R1) j- (A2) 1] i- (R3) g-OH (3) wherein A 1 and A 2 are single-core or polygon-divalent alicyclic hydrocarbon groups optionally substituted with alkyl groups such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl and the like (preferably alkyl groups having a maximum of 4 c ar bona toms), or halogen atoms, i.e. chloro, bromo, iodo or fluoro, 10 or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy and ling (preferably alkoxy groups having a maximum of 4 carbon atoms. Preferably, A 1 and A 2 are unsubstituted or substituted by halogen atoms. for the sake of flame resistance properties, k and 1 are 0 or 1, except that k and 1 are not 0. have the same meaning as defined by the general formula (1), preferably a methylene group or ethylene group or isopropylene group for the sake of flame resistance properties, j is 0 or 1. R 2 and 20 R 3, which may be the same or different, are alkyl groups such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl and the like, preferably alkyl groups having a maximum of 6 carbon atoms. f and g are 0 or 1, preferably 0. i is 0 or an integer greater than 0, preferably 0 or 1.

Particularly preferred polyhydric polycyclic alcohols (F-2) are divalent polycyclic alcohols of the following general formula (3-1): HO-A ^ fR ^ j-A2-0H (3-1) wherein A ^, A2, R1 and j has the same meaning as in the general formula (3).

Preferred examples of such divalent polycyclic alcohols are optionally substituted bicycloalkanediols such as 4,4'-bicyclohexanediol, 3,3'-bicyclohexanediol, octachloro-4,4'-bicyclohexanediol and the like, or bis- (hydroxycycloalkyl) alkanes such as 2,2-bis- (4-hydroxycyclohexyl) propane, 2,4'-dihydroxy-dicyclohexylmethane, bis- (2-hydroxycyclohexyl) methane, bis- (4-hydroxycyclohexyl) methane, bis- (4-hydroxy) methane 2,6-dimethyl-3-methoxycyclohexyl) -methane, 1,1-bis- (4-hydroxycyclohexyl) -ethane, 1,1-bis- (4-hydroxycyclohexyl) -propane, 1,1-bis- (4) -hydroxycyclohexyl) -butane, 1,1-bis- (4-hydroxycyclohexyl) -pentane, 2,2-bis- (4-hydroxycyclohexyl) -butane, 2,2-bis- (4-hydroxycyclohexyl) -pentane, 3,3-10 bis (4-hydroxyclohexyl) -pentane, 2,2-bis- (4-hydroxycyclohexyl) -heptane, bis- (4-hydroxycyclohexyl) -phenylmethane, bis- (4,4-hydroxycyclohexyl) -cyclo-hexylmethane, 1,2-bis- (4-hydroxycyclohexyl) -1,2-bis- (phenyl) -propane, 2,2-bis- (4-hydroxycyclohexyl) -1-phenylpropane, 2,2-bis-4 (4) -hydroxy-3-m ethylcyclohexyl) propane, 2,2-bis (4-hydroxy-2-methyl-cyclohexyl) propane, 2,2-bis- (4-hydroxy-2-methyl-cyclohexyl) -propane, 1,2-bis- 4-hydroxycyclohexyl) ethane, 1,1-bis- (4-hydroxy-2-chloro-cyclohexyl) -ethane, 1,1-bis- (3,5-dimethyl-4-hydroxycyclohexyl) ethane, bis- (3-methyl-4-hydroxycyclohexyl) propane, 2,2-bis- (3,5-dichloro-4-hydroxycyclohexy 1) propane, 2,2, bis (3-phenyl-4-hydroxycyclohexyl) propane , 2,2-bis (3-isopropyl-4-hydroxycyclohexyl) propane, 2,2-bis- (2-isopropyl-4-hydroxycyclohexyl) propane, 2,2-bis- (4-hydroxyperhydro-naphthyl) ) propane and the like, dihydroxycycloalkanes such as 4,4'-dihydroxydicyclohexane, 2,2-dihydroxybicyclohexane, 2,4-dihydroxybicyclohexane and the like, di- (hydrocycloalkyl) sulfones such as bis- (4-hydroxycyclohexyl) sulfon 4'-dihydroxy-dicyclohexylsulfone, 5-chloro-2,4-dihydroxydicyclohexylsulfone, 5-chloro-4,4'-dihydroxydicyclohexylsulfone, 3'-chloro-4,4'-dihydro-cyclohexylsulfone and the like, di (hydroxycycloalkyl) ethers such as bis (4-hydroxycyclohexyl) ether, 4.3 '- (or 4,2'-, 2,2'- or 2,3'-) dihydroxydicyclohexyl ether, 4,4'-dihydroxy-2,6-dimethyldicyclohexyl ether, bis- (4-hydroxy-3) -isobutylcyclohexyl) ether, bis- (4-hydroxy-3-isopropylcyclohexyl) ether ^ bis- (4-hydro-3-chloro-cyclohexyl) -ether, bis- (4-hydroxy-3-fluorocyclohexyl ether, bis - (4-hydroxy-3-bromocyclohexyl) ether, bis- (4-hydroxy-perhydronaphthyl) ether, bis- (4-hydroxy-3-chloro-perhydronaphthyl) ether, bis- (2-hydroxybicyclohexyl) ether , 4,41-dihydroxy-2,6-dimethoxydicyclohexyl ether, 4,4'-dihydroxy-2,5-diethoxydicyclohexyl ether and the like, 1,1-bis- (4-hydroxycyclohexyl) -2-phenylethane, 1, 3,3-trimethyl-1- (4-hydroxycyclohexyl) -6-hydroxyindane, 2,4-bis- (p-hydroxycyclohexyl) -4-methyl-ΙΟ-pentane.

A preferred group of such divalent polycyclic alcohols are compounds of the following general formula (3-2): HO-A1 ~ (R ^) j-A2 ~ (R ^) j-A2 ~ OH (3-2) wherein A 1, R 1 and j have the same meaning as defined by the general formula (3) and two R 2, two j and two A 2 are the same or different.

Examples of such divalent polycyclic alcohols are 1,4-bis (4-hydroxycyclohexylmethyl) -cyclohexane, 1,4-bis (4-hydroxy-cyclohexylmethyl) -tetra-methylcyclohexane, 1,4-bis (4-hydroxycyclohexylmethyl) -tetra -ethylcyclohexane, 1,4-bis (p-hydroxycyclohexy1-iso-propyl) -cyclohexane, 1,3-bis (p-hydroxycyclohexy-1-isopropyl) -cyclohexane and the like.

Another preferred group of such divalent polycyclic alcohols are compounds of the following general formula (3-3): H0-R2-A1- (Itjj j-A2-R3-OH (3-3) wherein Alf A2, R1, R2 , R3 and j have the same meaning as given by formula (3).

Examples of such divalent polycyclic alcohols are optionally substituted dihydroxyalkylbicycloalkanes such as 4,4'-dihydroxymethylbicyclohexane and optionally substituted bis (hydroxyalkylcycloalkyl) alkanes such as 1,2-bis (4-hydroxymethylcyclohexyl) bis (4-hydroxymethylcyclohexyl) propane, 2,3-bis (4-hydroxymethylcyclohexyl) butane, 2,3-dimethyl-2,3-bis- (4-hydroxymethylcyclohexyl) butane and the like.

The polyhydroxyl compound (G) is obtained by reacting the above-mentioned polyhydric alcohols (F) with at least one alicyclic ring with an alkylene oxide in the presence of catalysts that accelerate the OH group's reaction with the epoxy group and having atomic groups -ROH (wherein R is an alkyl group derived from an alkylene oxide) and / or - (R0) nH (wherein R is an alkylene group derived from an alkylene oxide such that a polyoxyalkylene chain may contain different alkylene groups and n is an integer of 2 or 15 more / which denotes the number of polymerized Oxyalkylene groups) there bonded to said phenol residue with an ether bond.

In this case, the ratio of alkylene oxide to polyhydric alcohols (F) is greater than 1: 1 (mol: mol).

Preferably, however, the ratio of the alkylene oxide to the OH group in the polyhydric alcohol (F) is 1 to 10: 1 or, in particular, 1 to 3: 1 according to equivalents. The alkylene oxides include e.g. ethylene oxide, propylene oxide and butylene oxide, and particularly preferred, are those which will produce branched chains in the production of ether bonds during their reaction with polyhydric phenols. Preferred examples thereof include propylene oxide and 2,3-butylene oxide, and a particularly preferred example thereof is propylene oxide.

A particularly preferred group of the polyhydroxyl compounds (G) are compounds of the following general formula:

H (0R) 0-A .- (R.).-A - O (RO) H

n ^ 1 1 3 2 n2 wherein A ^, Aj, j and R ^ have the same meaning as given by formula (3-1), R is an alkylene group of 2-4 carbon atoms and n ^ and n2 are from 1 -3.

18 DK 171533 B1

In addition, a preferred group of the polyhydroxyl compounds (G) compounds is the following general formula:

H (OR) O-Aj - (R-1) j “A2“ (Ri) j 0 (R0) n0H

wherein A 1, A 2, 3 R 1 have the same meaning as defined by formula (3-2), R is an alkylene group of 2-4 carbon atoms and n1 and n2 are from 1-3.

A particularly preferred group of the polyvalent single or polynuclear alcohols (F) are alcohols with one or two cyclohexane rings as an alicyclic ring, e.g. 2,2-bis (4-hydroxycyclohexyl) propane.

The epihalohydrine (s) is represented by the following general formula (4): X'-CHO-I-CH

V

Wherein Z is a hydrogen atom, a methyl group or an ethyl group and X 'is a halogen atom.

Examples of epihalohydrins (e) include e.g. epichlorohydrin, epibromohydrin, 1,2-epoxy-2-methyl-3-chloropropane, and 1,2-epoxy-2-ethyl-3-chloropropane.

Examples of acid catalysts which can be used to accelerate the reaction of epihalohydrins (e) with polyhydric phenols (D), polyhydroxyl compounds (E), polyhydric alcohols (F) or polyhydroxyl compounds (G) Lewis acids such as boron trifluoride, stannous chloride zinc chloride and ferric chloride, active derivatives of Lewis acids such as boron trifluoride etherate and mixtures thereof.

Examples of basic catalysts that can be used to accelerate the reaction between epihalohydrin (s) and polyhydric phenols (D), polyhydric alcohols (F) or polyhydroxyl compounds (G) include, for example. alkali metal hydroxides such as sodium hydroxide, alkali metal alcoholates such as sodium ethylate, tertiary amines such as triethylamine and triethanolamine, quaternary anroium compounds such as tetramethylammonium bromide, and mixtures thereof.

Examples of basic compounds which can be used to prepare glycidyl ethers while reacting epihalohydrins (e) with polyhydric phenols (D), polyhydric alcohols (F) or polyhydroxyl compounds (G), or for the preparation of glycidyl ethers ethers In the dehydrohalogenation of halohydrin ethens obtained by reacting epihalohydrins (e) with polyhydric Phenols (D), e.g. alkali metal hydroxides such as sodium hydroxide, alkali metal aluminates such as sodium aluminate and the like.

These catalysts or basic compounds can be used as they are or in the form of solutions in suitable inorganic and / or organic solvents.

The acid catalysts have high catalytic effect among the catalysts which can be used to accelerate the reaction of epihalohydrins (e) with polyhydric phenols (D), polyhydroxyl compounds (E), polyhydric alcohols (F) or polyhydroxy compounds (G).

Furthermore, polyglycidyl ethers obtained by converting epihalohydrins and a mixture of the above-mentioned polyhydric alcohols can be used as epoxy compounds.

Examples of epoxidized polyunsaturated compounds (A-1-4) include, for example,. epoxidized ... polybutadiene (named oxirone), vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (3,4-epoxy-cyclohexylmethyl) phthalate, diethylene-glycol-bis (3,4-epoxy-cyclohexane carboxylate), 3,4-35 epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexane carboxylate and ethylene glycol bis (3,4-epoxy-tetrahydrodicyclcentadien-8-yl) ether.

20 DK 171533 B1

In addition, well-known epoxy resins containing adjacent epoxy groups, e.g. various epoxy resins described in various places in the literature such as "Production and Use of: Epoxy 5 Resins" (edited by Hiroshi Kakiuchi), published by Shokodo, Tokyo (1970) are used.

Among these epoxy resins (A-1), a glycidyl ether having an epoxy equivalent of 180-1000 is preferred.

Preferred examples of the phosphorus-containing acids 10 are orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphoric acid, polyphosphoric acid, phosphonic acid, phosphinic acid, etc. The most preferred example is orthophosphoric acid.

The esters of phosphorus-containing acids are esters of the above-mentioned phosphorus-containing acids. Preferred examples are alkyl esters having one or more C ^ to Cg alkyl groups and at least one hydroxy group as well as hydroxyalkyl esters.

Preferred (hydroxy) alkyl groups are ethyl, propyl, n-butyl, 2-ethylhexyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, etc.

Among these, the most preferred esters are n-butyl or 2-ethylhexyl mono or diphosphates.

The salts of the phosphorous acids are the salts of the above phosphoric acids. Examples of the salts are salts of potassium, sodium, lithium, calcium, zinc, aluminum, tin, barium, etc. Preferred examples are the salts of potassium, sodium or calcium mono or diphosphates.

A preferred reaction ratio of the phosphoric acids (A-2) to the epoxy resin (Al) is 0.05 to 0.9, especially 0.05 to 0.4, expressed by an equivalent ratio of the hydroxy group in (A-2) to the epoxy group of (Al ).

It is preferred that the average epoxide equivalent in the modified epoxy resin (prepolymer) is less than 3000.

21 DK 171533 B1

The polyol resin (A) of the present invention is obtained by reacting the prepolymer and one or more compounds with amino groups (A-3) such as a primary or secondary amine. A preferred compound having 5 amino group (A-3) includes hydroxyamines having one or more hydroxy groups.

Examples of primary amines are methylamine, ethylamine, propylamine, etc. Examples of secondary amines are dibutylamine, etc. Examples of hydroxyamines 10 are ethanolamine, propanolamine, diethanolamine, diiSQ-propanolamine, etc.

A preferred reaction ratio of the amino compound (A-3) to the prepolymer is 1.1 to 0.7, preferably 1.0 to 0.9, expressed by an equivalent ratio of the group of (A-3) which is reactive with the epoxy group and the epoxy group in the prepolymer.

The reaction between the prepolymer and the compound with one or more amino groups (A-3) can be carried out without the use of any catalyst, e.g. 60-150 ° C.

The compound having more than one isocyanate group or groups that change to isocyanate groups under the curing conditions (B) includes, e.g. tolylene diisocyanate, xylylene diisocyanate, crude diphenylmethane diisocyanate, hexamethylene diisocyanate, an adduct of 3 moles of tolylene diisocyanate and trimethylol propane and isocyanate group-containing prepolymer obtained from the above compounds.

A ratio of the polyol resin (A) to the compound having more than one isocyanate group 30 or groups changing to isocyanate groups under the curing conditions (B) of 0.4 to 1.2 is preferred, preferably 0.7 to 1.0, expressed in equivalent ratio of hydroxy groups in (A) to isocyanate groups in (B). The bituminous material (C) includes coal tar, 35 coal tar pitches, various tar types, bojuntan, asphalt and white tar.

22 DK 171533 B1

The substituents for the bituminous material (C) include various materials, i.e. aromatic oil resins, coumarone resins, petroleum resins, diluents such as dioctyl phthalate, dibutyl phthalate, and highly boiled neutral oil from mineral oil, coal or the like.

The ratio between the bituminous material and / or its substitutes (C) and the polyol resin (A) is suitably between 0.5 and 2, expressed as a weight ratio between (C) and (A).

Other resins, diluents, solvents, colorants, curing catalysts, dewatering agents, pigments, anti-corrosive pigments such as glass flakes, fillers and other additives may be incorporated into the coating material of the invention if necessary.

The coating material can be cured under ambient conditions. However, if necessary, it can cure 20 under higher temperatures.

In the following examples, the term "parts" indicates parts by weight.

Preparation Example 1 25 parts of diglycidyl ether of bisphenol-A with an epoxy equivalent of 260, 25 parts of "ADEKA GLYCIROL ED501" with epoxy equivalent of 300, 33 parts of xylene and 6 parts of orthophosphoric acid are mixed together and reacted at 80 ° C for 5 hours. A prepolymer (I) of 80 wt% solids is obtained. 100 parts prepolymer (I) and 22 parts dibutylamine are mixed together and reacted at 80 ° C for 2 hours with stirring. A polyol resin (1) having a hydroxy group equivalent of 290 is obtained.

35 23 DK 171533 B1

Preparation Example 2 100 parts of diglycidyl ether of bisphenol-A having an epoxide equivalent of 470, 5 parts of ethyl phosphate and 35 parts of xylene are mixed and reacted at 90 ° C for 4 hours with stirring. A prepolymer (II) of 75 wt% solids is obtained. 100 parts of prepolymer (II) and 14 parts of diethanolamine are mixed with each other and reacted at 70 ° C for 3 hours with stirring. A polyol resin (2) having a hydroxy group equivalent of 350 is obtained.

10

Preparation Example 3 100 parts of diglycidyl ether of bisphenol-F (epoxy equivalent = 280), 50 parts of diglycidyl ether of propylene oxide adducts of bisphenol-A (epoxy equivalent = 15 340), 70 parts of xylene and 17 parts of dicalcium phosphate are mixed and reacted at 110 ° C for 5 hours. A prepolymer (III) of 70 wt% solids is obtained. 100 parts prepolymer (III) and 28 parts diisopropanolamine are mixed together and reacted at 80 ° C for 2 hours with stirring. A polyol-resin having a hydroxy group equivalent of 370 is obtained.

Preparation Example 4 100 parts diglycidyl ether of bisphenol-A having an epoxy equivalent of 260, 25 parts "ADEKA GLYCIROL ED-25 501" having an epoxy equivalent of 300, 30 parts xylene and 58 parts dibutylamine are mixed and reacted at 80 ° C for 2 hours. A polyol resin (4) having a hydroxy group equivalent of 210 is obtained.

Preparation Example 5 100 parts of diglycidyl ether of bisphenol-A with an epoxy equivalent of 470, 55 parts of xylene and 22 parts of diethanolamine are mixed together and reacted at 70 ° C for 3 hours with stirring. A polyol resin 35 (5) having a hydroxy group equivalent of 270 is obtained.

24 DK 171533 B1

Preparation Example 6 100 parts of diglycidyl ether of bisphenol-F having an epoxy equivalent of 280, 50 parts of diglycidyl ether of propylene oxide adducts of bisphenol-A with an epoxide equivalent of 340, 70 parts of xylene and 67 parts of diisopropanolamine are mixed and reacted at 80 ° C. 2 hours.

A polyol resin (6) having a hydroxy group equivalent of 190 is obtained.

Examples 1-6

Saira Comparative Examples 1-6 Coating materials were prepared with the polyol resins (1) - (6) obtained by the above-mentioned preparation examples. Components of the respective materials 15 are listed in Tables 1 and 2.

Each coating material is applied to a rusted steel sheet at a thickness of 150-200 µm. The steel plate has been exposed to outdoor conditions for a year and treated to remove the built up rust to the quality 20 DSal in SIS. The coating is cured for one week at room temperature.

The results of the test coatings (Examples 1-6) for adhesion and anticorrosive properties are better than the results for the 25 known materials (Comparative Examples 1-6), as shown in Tables 1 and 2.

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Claims (4)

Anticorrosive coating material, characterized in that it comprises (A) a polyol resin obtained by reacting a prepolymer of an epoxy resin (A1) and a phosphorus-containing compound (A-2) with at least one P-OH group selected from the group consisting of phosphorus acids, their esters, their salts and mixtures thereof, and one or more compounds (A-3) having one or more amino groups reactive with 10 epoxy groups, (B) a compound having more than one isocyanab group or groups which is changed to isocyanate groups under curing conditions, and (C) a bituminous material and / or its substitute. Coating material according to claim 1, characterized in that the prepolymer is obtained at an equivalent ratio of the hydroxy group of (A-2) to the epoxy group of (Al) of 0.05 to 0.9 and has an epoxy equivalent of preferably less than average 3000. Coating material according to claim 1 or 2, characterized in that the polyol is obtained with an equivalent ratio of the amino groups of the amino compound (A-3) to the epoxy groups of the prepolymer of 1.1 to 0.7. Coating material according to any one of claims 1, 2 and 3, characterized in that equivalent ratios between the hydroxy group in (A) and the isocyanate group in (B) are from 0.04 to 1.2 and that weight ratio between ( C) and (A) are from 0.5 to 2. 35