JPH07292027A - Film-formable chelate-forming resin - Google Patents

Abstract

PURPOSE:To obtain a film-formable chelate-forming resin being capable of used as a nonpolluting surface treatment as a substitute for an inorganic surface treatment and having excellent anticorrosiveness by forming a resin having specified chelate-forming groups. CONSTITUTION:This resin is the one having in the molecule at least one chelate- forming group represented by formula II (wherein R<3> is H, methyl or a direct bond) and obtained by the addition reaction of the amino group of a compound represented by formula I (wherein R<1> is H, a halogen, nitro, nitroso, cyano or a 18 C or lower (oxygenous) organic group; and R<2> is H or methyl) with the 1,2-epoxy group of a compound having a 1,2-epoxy group. Desirable examples of the base resins include an acrylic resin, an epoxy resin, a polyester resin, an alkyd resin, and a silicon-containing resin. this resin is used after it is converted into water-soluble or water-dispersible one by neutralizing it with an acid to an amine value of e.g. 30-180.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming resin capable of preventing metal corrosion by forming a strong metal chelate complex on a metal surface, a method for producing the same, and use thereof. INDUSTRIAL APPLICABILITY The resin according to the present invention can be used as a surface treatment agent or a resin for anticorrosion paint used for the purpose of modifying and protecting the surface of a metal corroded in a normal living environment.

[0002]

2. Description of the Related Art Conventionally, in order to prevent metal corrosion, (1) a surface treatment agent for forming an inorganic coating such as phosphate or chromate on the surface of a metal material, and (2) an epoxy resin. The technology of coating corrosion protection by applying an organic coating such as a phenol resin has been used.

However, in the case of the surface treatment agent, there is a drawback that environmental pollution caused by waste liquid of heavy metals, use of poisonous substances such as acids, alkalis, and cyanogens requires complicated steps. Further, in the case of coating film corrosion protection, there is a problem that the binding force between the organic coating film and the metal is not strong enough to completely suppress the corrosion reaction. Because no pollution-free and economical anticorrosion technology has been established, trillions of yen of metal resources are rusted and lost every year.

[0004]

In view of the above situation, the present inventor can use an inorganic surface treatment agent such as a phosphate or a chromate as a pollution-free surface treatment agent, and has an excellent anticorrosion property. In order to obtain a non-polluting resin exhibiting properties, we have been conducting research by comprehensively applying surface chemistry, thermodynamics, electrochemistry, complex chemistry, etc.

As a result, focusing on the fact that a polymer compound capable of forming a chelate complex binds to a metal much more strongly than a resin such as an epoxy resin or a phenol resin, a polymer compound capable of forming a chelate complex will be examined. I advanced. As a result, by having at least one specific chelate forming group in which the nitrogen atom is bonded to the ortho position with respect to the aromatic carboxyl group in one molecule, the binding energy with the metal due to chelation forms the corrosion reaction energy. It has been found that the coating film made of this resin exhibits excellent anticorrosion property because it exceeds the above limit and the charge of metal ions can be neutralized. Thus, the present invention has been completed.

That is, the present invention comprises an addition reaction by reacting an amino group of a compound represented by the following formula [1] with a 1,2-epoxy group in a compound having a 1,2-epoxy group. A chelate-forming resin capable of forming a film having at least one chelate-forming group represented by the following formula [2] in the molecule.

[0007]

[Chemical 4]

(Wherein R ¹ is the same or different and represents a hydrogen atom, a halogen atom, a nitro group, a nitroso group, a cyano group or an organic group which may contain an oxygen atom having 18 or less carbon atoms. , R ² represents a hydrogen atom or a methyl group.)

[0009]

[Chemical 5]

(Wherein R ¹ has the same meaning as above,
R ³ represents a hydrogen atom, a methyl group or a direct bond. )

The present invention also provides an aqueous solution of the above chelate-forming resin, a chelate-forming resin composition prepared by mixing the resin with a cross-linking agent, and the like.

Furthermore, the present invention is characterized in that the amino group of the compound represented by the above formula [1] is reacted with the 1,2-epoxy group in the compound having a 1,2-epoxy group to effect an addition reaction. A method for producing the above chelate-forming resin is provided.

The chelate-forming resin of the present invention undergoes an addition reaction by reacting the amino group of the compound represented by the above formula [1] with the 1,2-epoxy group in the compound having a 1,2-epoxy group. It is a chelate-forming resin capable of forming a film, in which at least one chelate-forming group represented by the above formula [2] is introduced into the molecule.

The organic group which may contain an oxygen atom in R ¹ of the compound represented by the above formula [1] has 18 or less carbon atoms, preferably 8 or less carbon atoms, and is an alkyl group. , An alkoxyalkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an aromatic hydrocarbon group containing an oxygen atom, and a hydrocarbon that forms a naphthalene ring together with the benzene ring in the compound represented by the above formula [1]. Groups and the like are included.

An alkyl group, an alkoxyalkyl group represented by R ¹ of the chelate-forming group represented by the above formula [1],
Specific examples of the cycloalkyl group, the aralkyl group, the aryl group, and the aromatic hydrocarbon group containing an oxygen atom are shown below. The alkyl group may be a straight chain or a branched chain,
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group and n
-Octadecyl group and the like; alkoxyalkyl group such as a 2-methoxyethyl group and 3-methoxypropyl group; a cycloalkyl group such as
Cyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group and the like; aralkyl group, for example, benzyl group, 4-methylbenzyl group, 4-isopropylbenzyl group, phenethyl group, etc .; aryl group, for example, phenyl group, diphenyl Group, naphthyl group,
Examples thereof include a 4-methylphenyl group, and examples of the aromatic hydrocarbon group containing an oxygen atom include a divalent group represented by the following formula.

[0016]

[Chemical 6]

Typical examples of the compound represented by the above formula [1] are anthranilic acid, N-methylanthranilic acid, 3-amino-2-naphthoic acid, 1-amino-2-naphthoic acid and 2-amino-1. -Naphthoic acid, 1-aminoanthraquinone-2-carboxylic acid and the like can be mentioned, and of these, anthranilic acid and N-methylanthranilic acid are particularly preferable. These compounds may be used alone or in combination of two or more in the reaction with the compound having a 1,2-epoxy group.

The 1,2-epoxy group-containing compound has at least one 1,2-epoxy group in the molecule, and the 1,2-epoxy group is represented by the above formula [1].
Any compound capable of undergoing an addition reaction with an amino group in the compound represented by the above, and the compound having a 1,2-epoxy group may be a low to high molecular weight compound having a 1,2-epoxy group in the molecule. Up to and including compounds.

Examples of the compound having a 1,2-epoxy group include glycidyl (meth) acrylate, 3,
1,2-epoxy group-containing polymerizable unsaturated monomer such as 4-epoxycyclohexylmethyl (meth) acrylate and allyl glycidyl ether; co-polymerization of the above 1,2-epoxy group-containing polymerizable unsaturated monomer with other polymerizable monomer Polymer polymers; various epoxy compounds such as aliphatic, alicyclic or monocyclic aromatic epoxy compounds, polyphenol type epoxy compounds, and epoxy group-containing silicon compounds;
Examples thereof include modified polyester resin and modified alkyd resin having an epoxy group.

"(Meth) acrylate" in the above monomer names means "methacrylate" or "acrylate". The same applies hereinafter.

Other polymerizable monomers forming a copolymer with the epoxy group-containing polymerizable unsaturated monomer in the above copolymer polymer include, for example, methyl (meth).
C of (meth) acrylic acid such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate _{1- C18} alkyl ester; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate (meth)
Hydroxyl group-containing unsaturated monomers such as C ₂ -C ₈ hydroxyalkyl esters and allyl alcohol acrylate; styrene, alpha-methyl styrene, aromatic vinyl compounds such as vinyl toluene, 2-hydroxyethyl (meth) acrylamide, dimethylaminoethyl A polymerizable unsaturated monomer having a secondary or tertiary amino group such as propyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid And acid group-containing unsaturated monomers such as maleic acid and fumaric acid; monomers such as vinyl acetate, (meth) acrylamide, (meth) acrylonitrile, and N-methylol (meth) acrylamide butyl ether. Alone again Can be used in combination of two or more.

The copolymerization of the epoxy group-containing polymerizable unsaturated monomer with another polymerizable monomer for obtaining the above-mentioned copolymer polymer can be carried out by a known copolymerization method. For example, the above-mentioned components are polymerized. It can be carried out by heating the reaction in the presence of a catalyst and preferably an organic solvent.

Aliphatic in the various epoxy compounds,
Specific examples of the alicyclic or monocyclic aromatic epoxy compound include 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-octylene oxide, styrene oxide, glycidyl acetate, glycidyl laurate, and CARDURA. E10 (cardura E10, glycidyl ester of branched higher fatty acid versatic acid, manufactured by Shell Chemical Co.), butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether, p-
t-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, 3,4-epoxycyclohexanecarboxylate, glycerin diglycidyl ether, dicyclopentadiene dioxide , 2,3-epoxy-2-ethylhexanol and the like.

As the polyphenol type epoxy compound in the above various epoxy compounds, those having a molecular weight of 200 to 4,000 obtained by the reaction of the polyphenol compound and epichlorohydrin are preferably used. Examples of the polyphenol compound include bis (4-hydroxyphenyl) -methane, bis (4-hydroxyphenyl) -2,2-propane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,
1-ethane, bis- (4-hydroxyphenyl) -1,
1-isobutane, bis (4-hydroxy-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane,
Bisphenol compounds such as 4,4′-dihydroxydiphenyl sulfone; and tetra (4-hydroxyphenyl) -1,1,2,2-ethane, phenol novolac, cresol novolac and the like.

The above polyphenol type epoxy compound may be one partially reacted with a polyol, a polyether polyol, a polyester polyol, a polyamidoamine, a polycarboxylic acid, a polyisocyanate compound or the like, and furthermore, ε-caprolactone or acryl. It may be one obtained by graft-polymerizing a monomer or the like.

Examples of the epoxy group-containing silicon compound in the various epoxy compounds include silane compounds represented by the following general formula [3], one or more partial condensates of these silane compounds, and these silane compounds and ethers. A partial cocondensation product with another silane having a silanized group and the like can be preferably used.

[0027]

[Chemical 7]

[Wherein A represents a 1,2-epoxy group-containing hydrocarbon group or a glycidyloxyalkyl group, X represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon number of 1 to 1]
An alkoxy group having 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms or an alicyclic hydrocarbon oxy group having 5 to 8 carbon atoms is shown. Y and Z are the same or different and each has 1 to 1 carbon atoms.
8 alkoxyl groups, 6-8C aryloxy groups, or 5-8C alicyclic hydrocarbonoxy groups are shown, which may be the same as X. ]

The 1,2-epoxy group-containing hydrocarbon group in A above preferably has 2 to 10 carbon atoms,
The glycidyloxyalkyl group preferably has 4 to 15 carbon atoms. As a preferable example of the above A, γ-
Examples thereof include a glycidoxypropyl group and a β- (3,4-epoxycyclohexyl) -ethyl group.

In the above X, Y and Z, the number of carbon atoms is 1 to 1.
Among the eight alkoxyl groups, the aryloxy group having 6 to 8 carbon atoms, and the alicyclic hydrocarbon oxy group having 5 to 8 carbon atoms, preferred ones include, for example, methoxy, ethoxy, propoxy, butoxy, hexoxy, Octoxy,
Examples thereof include an alkoxyl group having 1 to 8 carbon atoms such as a methoxyethoxy group, a phenoxy group and a cyclohexyloxy group.

In the above X, among the hydrocarbon groups having 1 to 18 carbon atoms, preferable ones are those having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl. An alkyl group having 6 to 8 carbon atoms such as phenyl, methylphenyl and ethylphenyl; and an alicyclic hydrocarbon group having 5 to 8 carbon atoms such as cyclopentyl and cyclohexyl.

Typical examples of the silane compound represented by the above general formula [3] include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane can be mentioned.

Other silane compounds having an etherified silanol group which can be partially co-condensed with the silane compound represented by the above formula [3] include silane compounds having two or more etherified silanol groups. Can be used, for example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, ethyltrimethoxysilane,
Examples thereof include silane compounds such as dimethyldimethoxysilane and diphenyldimethoxysilane, and partial cocondensates of these silane compounds.

Partial (co) condensation of the silane compound represented by the above formula [3] and partial cocondensation of the silane compound represented by the above formula [3] with another silane compound having an etherified silanol group are carried out. It can be carried out according to a conventionally known condensation method of an etherified silane compound, generally in the presence of an organic acid such as acetic acid, an acid such as an inorganic acid such as hydrochloric acid, and water, at a temperature from room temperature to a boiling point or less, preferably 50 to It can be performed by heating to 90 ° C. The amount of water may be appropriately increased or decreased depending on the degree of condensation.

The modified polyester resin or modified alkyd resin having a 1,2-epoxy group is, for example, a polyester resin or an alkyd resin having a hydroxyl group, and a polyepoxy compound having a 1,2-epoxy group at the hydroxyl group. It can be obtained by a method of reacting with to introduce an epoxy group into the resin.

In the chelate resin of the present invention, it is introduced by an addition reaction between the amino group of the compound represented by the above formula [1] and the 1,2-epoxy group in the 1,2-epoxy group-containing polymer or compound. Typical examples of the chelate-forming group represented by the above formula [2] include the following.

[0037]

[Chemical 8]

In the resin of the present invention, the chelate-forming group is a moiety that forms a stable 6-membered chelate complex of a nonionic intramolecular complex salt type with a +2 or +3 valent metal ion.

The above-mentioned chelating group is

[0040]

[Chemical 9]

The chelate complex to be formed is abbreviated as follows and it is as follows.

[0042]

[Chemical 10]

As described above, three sets of chelate-forming groups are bound to +3 valent metal ions, and two sets of chelate-forming groups are bound to +2 valent metal ions. Charge was neutralized by carboxy ion 6
It forms a chelate complex of the member ring. The formed chelate complex has a neutralized charge and is nonionic, so that a corrosion current does not easily flow against metal corrosion, and it has a 6-membered ring structure, which is structurally stable and excellent. Shows anticorrosive properties.

The resin of the present invention is required to have at least one, preferably 2 to 700, of the above-mentioned chelate-forming groups in one molecule. When a plurality of chelate-forming groups are contained in one molecule, a chelate is formed. In addition, three-dimensionalization of the resin coating progresses, a strong chelate bond is formed, and the crosslinking density of the resin coating also increases.

As a method for producing the resin of the present invention by introducing a chelate-forming group into the resin, for example, the following (a) to
The method of (d) etc. can be mentioned.

(A) A method in which the amino group of the compound represented by the formula [1] is added to the 1,2-epoxy group of the polymer having the 1,2-epoxy group.

(B) an addition reaction product obtained by addition-reacting the 1,2-epoxy group of the compound having the 1,2-epoxy group with the amino group of the compound represented by the formula [1];
A method of reacting a secondary hydroxyl group produced by an addition reaction in the reaction product with a polymer having a functional group such as an isocyanate group having reactivity. When the compound having a 1,2-epoxy group has a first functional group such as a hydroxyl group, 1,2 of the compound having a 1,2-epoxy group is
A 2-epoxy group is obtained by addition-reacting an amino group of the compound represented by the above formula [1] with an addition reaction product and a second functional group reactive with the first functional group in the reaction product. A method of reacting with a polymer having.

(C) The formula [2] obtained by adding the amino group of the compound represented by the formula [1] to the 1,2-epoxy group of the 1,2-epoxy group-containing polymerizable unsaturated monomer. A method for copolymerizing an addition reaction product having a chelate-forming group and a polymerizable unsaturated bond, and another polymerizable unsaturated monomer copolymerizable with the reaction product.

(D) A method of adding the amino group of the compound represented by the above formula [1] to the 1,2-epoxy group of the epoxy group-containing silicon compound. In addition, the compound having the chelate-forming group of the above formula [2] and the etherified silanol group obtained by this method is partially (co) condensed, or partially combined with another silane compound having an etherified silanol group. Cocondensation method.

In the above methods (a) to (d), 1,
The addition reaction for reacting the 2-epoxy group with the amino group of the compound represented by the above formula [1] is usually about 20 to 100 ° C.
Can be carried out for about 1 to 24 hours. When the amino group of the compound represented by the above formula [1] has two active hydrogens, only one 1,2-epoxy group may be added to one amino group, or 2
Individual pieces may be added.

In the method (b), a compound having a chelate-forming group represented by the above formula [2] and a functional group such as a hydroxyl group is first prepared, and the functional group (carboxyl group in the chelate-forming group in the compound is prepared. (Excluding groups) is reacted with a functional group in the polymer to increase the molecular weight. In the above method (b), the relationship between the secondary hydroxyl group and the second functional group reactive with the first functional group is as shown in Table 1 below. The second functional group should not react or react with the carboxyl group in the chelate forming group.

[0052]

[Table 1]

In the method (c), the above formula [2]
Other polymerizable unsaturated monomers used for copolymerization with the addition reaction product having a chelate-forming group and a polymerizable unsaturated bond include the 1,2-epoxy group-containing polymerizable unsaturated monomer and other In the copolymer polymer with the polymerizable monomer, the monomers exemplified as the other polymerizable monomer can be used. The copolymerization of the addition reaction product having the chelate-forming group of the above formula [2] and the polymerizable unsaturated bond with the other polymerizable unsaturated monomer can be carried out by a known copolymerization method. It can be carried out by reacting the components with heating in the presence of a polymerization catalyst and preferably an organic solvent.

In the method (d), the above formula [2]
Other silane compounds having an etherified silanol group used for partial co-condensation with a compound having a chelate-forming group and an etherified silanol group, include, in the section of the epoxy group-containing silicon compound, As the other silane compound having an etherified silanol group, which is used for partial cocondensation with the silane compound represented by the formula [3] to obtain a partial cocondensate, those exemplified can be used.

In the method (d), the compound having the chelate-forming group of the above formula [2] and the etherified silanol group is partially (co) condensed, or another compound having an etherified silanol group is used. The method of partial co-condensation with a silane compound can follow a conventionally known condensation method of an etherified silane compound, generally, an organic acid such as acetic acid, an acid such as an inorganic acid such as hydrochloric acid, and room temperature to boiling point in the presence of water. It can be carried out by heating to the following temperature, preferably 50 to 90 ° C. The amount of water may be appropriately increased or decreased depending on the degree of condensation.

The resin of the present invention obtained by the method (d) has an etherified silanol group, and this group reacts with moisture in the air to hydrolyze to form a silanol group and crosslink. It can be a so-called moisture-curing type that reacts.

Further, the resin obtained by the above method (a), (b) or (c) can be made into a moisture curing type by introducing an etherified silanol group into the resin. In order to introduce an etherified silanol group into the resin, for example, an alcoholic hydroxyl group is present in the resin, and a monoisocyanate compound having an etherified silanol group in the hydroxyl group is added, for example, in the presence of a tin catalyst. Further, a method such as reacting both at about 20 to 100 ° C. for about 1 to 10 hours can be used. Typical examples of the etherified monoisocyanate compound having a silanol group include γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.

The resin of the present invention may be obtained by a method other than the methods (a) to (d) and the modification methods thereof.

The resin of the present invention is required to have a film forming ability and has a number average molecular weight of about 500 to 500,0.
The range of 00 is preferable, and more preferably about 1,000 to 2
Suitably it is in the range of 0,000. Further, the resin of the present invention is required to have at least one chelate-forming group in the molecule, and the chelate-forming group is contained in an amount of 0.2 to 3.5 mol, more preferably 0.3 to
It is preferable to have 3.0 mol.

In the resin of the present invention, as the base resin, various kinds of resins can be used as described above, but from the viewpoint of film forming property, an acrylic resin, an epoxy resin, a polyester resin, an alkyd resin, Silicon containing resins are preferred.

The resin of the present invention may be diluted with an organic solvent before use, or the amount of amino groups in the resin may be adjusted to, for example, an amine value of 30 to 180, and the amino groups may be acidified.
For example, neutralize with organic acids such as formic acid, acetic acid, propionic acid, lactic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid,
It may be used by dispersing or dissolving it in water by chaotination. In addition, the amount of an acid group such as a carboxyl group in the resin is adjusted to, for example, an acid value of 30 to 130, the acid group is neutralized with a base such as an organic amine and ammonia,
It may be dispersed or dissolved in water by being anionized before use. In the case where the resin is chaotic, the amino group to be introduced into the resin may be a compound represented by the formula [1] which serves as a chelate-forming group,
It may be based on both the compound of formula [1] and an amino group-containing compound other than this compound.

As the amino group-containing compound other than the compound represented by the formula [1], aliphatic, alicyclic or aromatic-aliphatic primary or secondary amines (these react with an epoxy group An amino group), a tertiary aminomonoisocyanate obtained by the reaction of a tertiary amino alcohol and a diisocyanate (which can react with a hydroxyl group in a resin to introduce an amino group into the resin), and Examples thereof include a polymerizable unsaturated monomer having a secondary or tertiary amino group (for example, an amino group can be introduced into a resin by copolymerization in the method (c)).

Examples of the above primary or secondary amines include, for example: (a) methylamine, ethylamine, n- or iso.
-Primary monoamines such as propylamine, monoethanolamine, n- or iso-propanolamine; (b) diethylamine, diethanolamine, di-n-
Or a secondary monoamine such as -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine; (C) ethylenediamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylamine, Examples include primary or secondary polyamines such as dimethylaminopropylamine.

These primary or secondary amines are
When an epoxy group is present in the resin, it may be reacted with this epoxy group as it is, but in general, when a primary amine or N-hydroxyalkyl secondary amine among the above amines is used, this It is preferable to heat react with a ketone, an aldehyde or a carboxylic acid in advance at, for example, about 100 to 230 ° C. to modify it into an aldimine, ketimine, oxazoline or imidazoline, and use this. The reaction of these primary amine, secondary amine and modified amine with the epoxy group in the resin is carried out, for example, by heating at a temperature of about 80 to about 200 ° C. for about 2 to about 5 hours. You can

When the resin has a polymerizable unsaturated group, the amino group can be introduced by adding a primary amine to the polymerizable unsaturated group. This addition reaction is performed in the presence of both, for example, about 20 to 100 in the presence of an acid catalyst.
It can be carried out by reacting at about 1 to 24 hours.

When a tertiary aminomonoisocyanate is used as the amino group-containing compound, for example, 30 to 30
The reaction may be carried out at a temperature of about 120 ° C. by reacting with the alcoholic hydroxyl group in the resin until the absorption of the isocyanate group is completely eliminated by infrared absorption spectrum measurement.

Further, in order to introduce an amino group using a polymerizable unsaturated monomer having a secondary or tertiary amino group, for example, in the method of the above (c), the chelate-forming compound represented by the formula [2] is formed. A polymerizable unsaturated monomer having a secondary or tertiary amino group may be used as a part or all of the other polymerizable unsaturated monomer to be copolymerized with the compound having a group and a polymerizable double bond. .

When the resin is anionized, examples of the acid group to be introduced into the resin include a carboxyl group, a sulfonic acid group and a phosphoric acid group.

To introduce these acid groups into the resin, for example, an epoxy group is added to the resin, and a polybasic acid having an excessive molar amount of the above acid group is reacted with the epoxy group. Can be done. Examples of the polybasic acid include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, succinic acid, glutaric acid, adipic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) trimellitic acid, and pyrrolic acid. Examples include meritic acid.

As another method of introducing an acid group into the resin, for example, in the above method (c), another polymerizable unsaturated compound obtained by copolymerizing with a compound having a chelate-forming group and a polymerizable double bond is used. Examples thereof include a method of using an acid group-containing unsaturated monomer having the above acid group as a part or all of the monomers.

In the resin of the present invention, a reactive group such as a hydroxyl group is present in the resin in addition to the above chelate-forming group,
It can be used in combination with a crosslinking agent that reacts with this reactive group. For example, when the reactive group is a hydroxyl group, as a cross-linking agent, known polyisocyanate compounds, blocked polyisocyanate compounds and aminoplast resins, that is, urea, melamine, nitrogen-containing compounds such as benzoguanamine and formaldehyde A condensate with an aldehyde or a lower alkyl ether compound (the carbon number of the alkyl group is 1 to 4) of this condensate can be used to crosslink at room temperature or by heating. In addition, the presence of a hydroxyl group in the resin, a part of the hydroxyl group is reacted with a compound obtained by blocking one isocyanate group of the diisocyanate compound to introduce a blocked isocyanate group into the resin, thereby self-crosslinking It can be a resin having properties.

Further, a polymerizable unsaturated group is allowed to exist in the resin of the present invention, and the resin and the polymerizable unsaturated vinyl monomer are used in combination, and if necessary, a photopolymerization initiator is added. Thus, it is possible to obtain a composition which is cured by irradiation with an actinic ray such as an electron beam or an ultraviolet ray. As the polymerizable unsaturated vinyl monomer, a conventionally known vinyl monomer can be used, and examples thereof include those exemplified as the other polymerizable unsaturated monomers in the method (c), ethylene glycol di (meth). ) Polyfunctional monomers such as acrylate and trimethylolpropane tri (meth) acrylate. The introduction of the polymerizable unsaturated group into the resin may be carried out by allowing an epoxy group to exist in the resin and adding a carboxyl group-containing polymerizable unsaturated compound to the epoxy group.

The resin of the present invention may be either an organic solvent system or an aqueous system (kaoline system, anion system). In these systems, they may be used alone or in combination with a crosslinking agent, a vinyl monomer or the like. By adding a pigment, a surface conditioner, an oxidizing agent, etc. accordingly, it can be used as a metal surface treatment agent, an anticorrosion paint, or the like. These surface treatment agents and anticorrosion coatings are sprayed, brushed, roll-coated, dip-coated, kao-tin electrodeposition coating, anion electrodeposition coating on the substrate,
It is applied by dry dip automatic deposition, silk screen printing, etc. so that the dry film thickness is usually 0.1 to 50 μm.
Then it is dried and cured. When used as a surface treatment agent, the dry film thickness is preferably about 0.1 to 5 μm, and when used as an anticorrosion coating, the dry film thickness is preferably about 1 to 50 μm. Examples of the substrate to be applied include metals such as iron, zinc, copper and aluminum, and those obtained by subjecting the surfaces of these metals to surface treatment such as phosphate treatment or chromate treatment.

[0074]

INDUSTRIAL APPLICABILITY The resin of the present invention is capable of imparting excellent anticorrosion properties to metals that generate +2 or +3 metal ions due to corrosion of iron, zinc, copper, aluminum, etc., and is non-polluting. Is. Therefore, the resin of the present invention is extremely useful as a metal surface treatment agent or a coating for anticorrosion.

[0075]

EXAMPLES The present invention will be specifically described below with reference to examples. In the following, "parts" and "%" are based on weight unless otherwise specified.

Example 1 In a flask, 214.0 parts of propylene glycol monomethyl ether, Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 186), 186.0 parts and N-methylanthranilic acid were placed. 75.6 parts were charged and the mixture was heated with stirring at 60 ° C. for 5 hours. Next, 52.6 parts of 2,2′-iminodiethanol and 52.6 parts of propylene glycol monomethyl ether were added to this product, and the mixture was further stirred with heating at 60 ° C. for 3 hours, then cooled to room temperature and solid content was 50. % Chelate-forming resin solution was obtained. The obtained chelate-forming resin has a number average molecular weight of 630 and an amine value of 170, and has one chelate-forming group and four hydroxyl groups per molecule.

Example 2 A flask was charged with 254.6 parts of propylene glycol monomethyl ether, 186.0 parts of Epicoat 828 and 68.6 parts of anthranilic acid, and the mixture was heated with stirring at 60 ° C. for 5 hours. Next, 52.6 parts of 2,2′-iminodiethanol and 52.6 parts of propylene glycol monomethyl ether were added to this product, and the mixture was further stirred with heating at 60 ° C. for 3 hours, then cooled to room temperature and solid content was 50. % Chelate-forming resin solution was obtained. The obtained chelate-forming resin has a number average molecular weight of 616 and an amine value of 80,
It has one chelate-forming group and four hydroxyl groups per molecule.

Example 3 A flask was charged with 323.1 parts of propylene glycol monomethyl ether, 186.0 parts of Epikote 828 and 131.1 parts of anthranilic acid, and the mixture was heated with stirring at 60 ° C. for 8 hours and then cooled to room temperature. A chelate-forming resin solution having a solid content of 50% was obtained. The obtained chelate-forming resin has a molecular weight of 634 and an amine value of 177, and has two chelate-forming groups and two hydroxyl groups per molecule.

Example 4 A flask was charged with 288.9 parts of propylene glycol monomethyl ether, 186.0 parts of Epikote 828 and 102.9 parts of anthranilic acid, and the mixture was heated with stirring at 60 ° C. for 8 hours and then cooled to room temperature. A chelate-forming resin having a solid content of 50% was obtained. The chelate-forming resin obtained was a 1: 1 (molar ratio) mixture of molecular weight 634 and molecular weight 509, had an amine value of 140, and had an average of 1.5 chelate-forming groups per molecule. , Having 1.5 hydroxyl groups and 0.5 epoxy groups.

Example 5 133.1 parts of propylene glycol monomethyl ether, EX-830 [Nagase Kasei Kogyo Co., Ltd.] were placed in a flask.
Made, polyoxyethylene type epoxy resin, epoxy equivalent 262] 262.0 parts and anthranilic acid 131.1
Parts were charged, and the mixture was heated with stirring at 60 ° C. for 8 hours. Then, 93.0 parts of Epicoat 828 and 359.0 parts of propylene glycol monomethyl ether were added to this,
After heating and stirring at 60 ° C. for 8 hours, the mixture was cooled to room temperature to obtain a chelate-forming resin solution having a solid content of 50%. The obtained chelate-forming resin has a molecular weight of 1,94.
4, having an amine value of 100, and having 4 chelate-forming groups and 6 hydroxyl groups per molecule.

Example 6 In a flask, 173.1 parts of propylene glycol monomethyl ether, EX-841 [Nagase Kasei Co., Ltd.]
Made, polyoxyethylene type epoxy resin, epoxy equivalent 382] 382.0 parts and anthranilic acid 131.1
Parts were charged, and the mixture was heated with stirring at 60 ° C. for 8 hours. Then, 93.0 parts of Epicoat 828 and 439.1 parts of propylene glycol monomethyl ether were added to this, and 6
After heating and stirring at 0 ° C. for 8 hours, the mixture was cooled to room temperature to obtain a chelate-forming resin solution having a solid content of 50%. The obtained chelate-forming resin has a molecular weight of 2,424 and an amine value of 90, and has 4 chelate-forming groups and 6 hydroxyl groups per molecule.

Example 7 337.2 parts of butyl acetate, Epikote 82 in a flask
186 parts of 8 and 151.2 parts of N-methylanthranilic acid were charged and heated and stirred at 60 ° C. for 5 hours to give a solid content of 5
A 0% adduct solution was obtained. This adduct has a molecular weight of 643,
It has an amine value of 170 and has two chelate-forming groups and two hydroxyl groups in one molecule. Separately, 100 parts of butyl acetate was charged into the flask and kept at 120 ° C. A mixture of 13.8 parts of isocyanatoethyl methacrylate, 50.9 parts of ethyl methacrylate, 35.3 parts of N, N-dimethylacrylamide and 10 parts of 2,2'-azobisisobutyronitrile was added thereto over 2 hours. Dropped. After dripping, aging at 120 ℃ for 1 hour, solid content 50
% Isocyanate group-containing resin solution was obtained. This resin has a weight average molecular weight of about 1,500 and has an average of 1.2 isocyanate groups in one molecule. 643 parts of the adduct solution having a solid content of 50% is maintained at 60 ° C., and 1,500 parts of the isocyanate group-containing resin solution having a solid content of 50% is added dropwise thereto over 2 hours, and further 60 ° C.
And held for 1 hour to obtain a chelate-forming resin solution having a solid content of 50%. The resin obtained has a number average molecular weight of about 2,30.
It has an amine value of 0 and an amine value of 46, and has two chelate-forming groups and 0.8 hydroxyl groups on average in one molecule.

Example 8 20.5 parts of butyl acetate, 10 parts of glycidyl methacrylate and 10 parts of N-methylanthranilic acid were placed in a flask.
5 parts was added and the mixture was heated with stirring at 60 ° C. for 5 hours to obtain an adduct solution of glycidyl methacrylate having one polymerizable unsaturated double bond and one hydroxyl group and N-methylanthranilic acid. Into another flask, 100 parts of butyl acetate was charged and kept at 120 ° C., 41 parts of the adduct solution obtained above, 5 parts of 2-hydroxypropyl methacrylate,
A mixed solution of 85 parts of n-butyl methacrylate and 10 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour and then aged at 100 ° C. for 1 hour, then cooled to room temperature and the solid content was 50%. To obtain a chelate-forming resin solution. The obtained resin has a number average molecular weight of about 2,800 and an amine value of 32, and has two chelate-forming groups and three hydroxyl groups on average in one molecule.

Example 9 A flask was charged with 237 parts of γ-glycidoxypropyltrimethoxysilane, 151.2 parts of N-methylanthranilic acid and 388.2 parts of butyl acetate, and heated and stirred at 60 ° C. for 5 hours to give a solid content. A 50% chelate-forming resin solution was obtained. The obtained resin has a molecular weight of 388 and an amine value of 140, and has one chelate forming group, one hydroxyl group and three methoxysilyl groups in one molecule.

Example 10 Example 1 was added to a mixed solution of 400 parts of acetone and 4 parts of water.
100% chelate-forming resin solution having a solid content of 50%
Part, formic acid 4 parts and Neugen EA152 (Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant) 0.25 part,
After dissolution, 2,600 parts of water was gradually added to this and mixed uniformly. Next, the solvent was removed, and the reduced amount was added with water to obtain a surface treatment composition A having a solid content concentration of about 1.6%.

Example 11 Example 2 was added to a mixed solution of 400 parts of acetone and 4 parts of water.
100% chelate-forming resin solution having a solid content of 50%
Parts, a solution of methyl ethyl ketoxime blocked 4,4'-methylenebis (cyclohexyl isocyanate) with a solids content of about 60%, 28 parts, formic acid 4 parts and Neugen EA1.
0.33 parts of 52 was mixed and dissolved, and water 3,6
00 parts was gradually added and mixed uniformly. Next, the solvent is removed, and the weight loss is added with water to give a solid content of about 1.6%.
The surface treatment composition B of was obtained.

Example 12 Example 3 was added to a mixed solution of 400 parts of acetone and 4 parts of water.
100% chelate-forming resin solution having a solid content of 50%
Parts, solid content about 60% resol type phenolic resin 15
Parts, 0.3 parts of Neugen EA152 and 4.7 parts of amine-blocked paratoluenesulfonic acid solution (paratoluenesulfonic acid concentration 10%) were added and dissolved, and this was stirred in 3,200 parts of water. While gradually adding, the mixture was mixed uniformly. Then remove the solvent, add the weight loss with water,
The surface treatment composition C was obtained by adjusting the pH to about 4.5 with a 20% tartaric acid aqueous solution.

Example 13 Chelate-forming resin 10 having a solid content of 50% obtained in Example 4
90 parts of ethanol was added to the parts, and the mixture was stirred uniformly to obtain a solid content of 5
% Surface treatment composition D was obtained.

Example 14 The procedure of Example 10 was repeated except that the chelate-forming resin solution obtained in Example 5 was used instead of the chelate-forming resin solution obtained in Example 1, and the solid content was changed. A surface treatment composition E having a concentration of about 1.6% was obtained.

Example 15 The procedure of Example 10 was repeated except that the chelate-forming resin solution obtained in Example 6 was used instead of the chelate-forming resin solution obtained in Example 1, and the solid content was changed. A surface treatment composition F having a concentration of about 1.6% was obtained.

Example 16 A surface treatment was conducted in the same manner as in Example 12 except that the chelate-forming resin solution obtained in Example 8 was used in place of the chelate-forming resin solution obtained in Example 3. Composition G was obtained.

Test Examples 1 to 7 Surface treatment compositions A, B, C obtained in Examples 10 to 16
As shown in Table 1, various materials such as cold rolled steel sheet, iron-zinc alloy plated steel sheet, and aluminum sheet were dipped in the respective liquids D, E, F, and G, pulled up, and then dried to form a surface-treated film. Formed. The dry film thickness of the surface treatment film is about 0.5μ
It was m. Epoxy / melamine-based paint white (abbreviated as "EP / ME" in Table 1) was applied on each surface-treated film so that the dry film thickness was about 40 μm.
It was baked and cured at 40 ° C. for 30 minutes.

Test Example 8 The chelate-forming resin solution obtained in Example 7 was applied as a primer composition H onto various materials as shown in Table 1 with a bar coater to a dry film thickness of about 3 μm, 60 ° C
And dried for 20 minutes to form a primer film. SD Horus White [Kansai Paint Co., Ltd.,
A synthetic resin blend paint white (abbreviated as "SD" in Table 1)] was applied to a dry film thickness of about 100 μm, and dried at room temperature for 5 days.

Test Example 9 The chelate-forming resin solution obtained in Example 9 was used as a surface treatment composition I, and various materials were immersed in this solution as shown in Table 1 and pulled up, and then dried to obtain a surface treatment film. Was formed. The dry film thickness of the surface-treated film was about 0.5 μm. On this surface-treated film, Arestech 100 White [Kansai Paint Co., Ltd., polyester resin coating for advanced processing, white (abbreviated as "AT" in Table 1)] was dried with a bar coater to a dry film thickness of about 100. It was coated so as to have a thickness of 18 μm, and baked and cured for 60 seconds under the condition that the material reaching temperature was 225 ° C.

Comparative Test Examples 1 to 3 Instead of subjecting the material to the chelate-forming surface treatment, a zinc phosphate treated plate (Example 1), a chromic acid treated plate (Example 2) or an untreated plate (Example 3) was used. On top of this, the epoxy / melamine-based paint used in Test Examples 1 to 7 was applied as a topcoat paint so that the dry film thickness was about 40 μm, and baked and cured at 140 ° C. for 30 minutes.

Test Examples 1 to 9 and Comparative Test Examples 1 to 3
A salt water spray test was conducted on the coated plate obtained in 1. The test results are shown in Table 2.

Test method Salt water spray test (SST): A cross cut was put in a coated plate and the test was conducted according to JIS Z2371. The test time was 1,000 hours. The maximum length of the peeling width and the rusting width on one side of the cross cut portion of the coated plate after the test was evaluated, and this length was displayed.

[Table 2]

Front page continuation (72) Inventor Jun Suzuno 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. (72) Inventor Satoshi Maki 4-1-1, Higashi-Hachiman, Hiratsuka, Kanagawa In the company

Claims (5)

[Claims] 1. 1,2 in a compound having an amino group of a compound represented by the following formula [1] and a 1,2-epoxy group:
A chelate-forming resin capable of forming a film, having at least one chelate-forming group represented by the following formula [2] in the molecule, which is obtained by an addition reaction by a reaction with an epoxy group. [Chemical 1] (In the formula, R ¹ is the same or different and represents a hydrogen atom, a halogen atom, a nitro group, a nitroso group, a cyano group or an organic group which may contain an oxygen atom having 18 or less carbon atoms, and R ² Represents a hydrogen atom or a methyl group.) (In the formula, R ¹ is the same or different and represents a hydrogen atom, a halogen atom, a nitro group, a nitroso group, a cyano group or an organic group which may contain an oxygen atom having 18 or less carbon atoms, and R ³ Represents a hydrogen atom, a methyl group or a direct bond.) 2. The chelate-forming resin according to claim 1, wherein the base portion of the chelate-forming resin is an acrylic resin, an epoxy resin, a polyester resin, an alkyd resin, or a silicon-containing resin. 3. An aqueous solution of a chelate-forming resin obtained by neutralizing the chelate-forming resin according to claim 1, which has an amine value of 30 to 180, with an acid to make it water-soluble or water-dispersed. 4. A chelate-forming resin composition comprising the chelate-forming resin according to claim 1 and a crosslinking agent. 5. A 1,2-epoxy group-containing 1,2-epoxy group-containing compound represented by the following formula [1]:
-The method for producing a chelate-forming resin according to claim 1, wherein the addition reaction is carried out by a reaction with an epoxy group. [Chemical 3] (In the formula, R ¹ is the same or different and represents a hydrogen atom, a halogen atom, a nitro group, a nitroso group, a cyano group or an organic group which may contain an oxygen atom having 18 or less carbon atoms, and R ² Represents a hydrogen atom or a methyl group.)