WO1992013902A1 - Film-forming chelating resin, production thereof, use thereof, and formation of electrodeposition coating - Google Patents

Film-forming chelating resin, production thereof, use thereof, and formation of electrodeposition coating Download PDF

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Publication number
WO1992013902A1
WO1992013902A1 PCT/JP1992/000113 JP9200113W WO9213902A1 WO 1992013902 A1 WO1992013902 A1 WO 1992013902A1 JP 9200113 W JP9200113 W JP 9200113W WO 9213902 A1 WO9213902 A1 WO 9213902A1
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WO
WIPO (PCT)
Prior art keywords
parts
resin
group
chelate
forming
Prior art date
Application number
PCT/JP1992/000113
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Hideo Kogure
Heihachi Murase
Masafumi Kume
Original Assignee
Kansai Paint Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP3102182A external-priority patent/JPH05271330A/ja
Priority claimed from JP4247591A external-priority patent/JPH04258603A/ja
Priority claimed from JP3593591A external-priority patent/JPH04276098A/ja
Application filed by Kansai Paint Company, Limited filed Critical Kansai Paint Company, Limited
Priority to US07/930,524 priority Critical patent/US5342901A/en
Priority to DE4290288A priority patent/DE4290288C2/de
Publication of WO1992013902A1 publication Critical patent/WO1992013902A1/ja

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Classifications

    • 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
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • Chelate-forming resin capable of forming a film, its production method, its use, and method of forming an electrodeposition coating film
  • the present invention relates to a chelate-forming resin capable of forming a novel film, a method for producing the same, a use thereof, and a method for forming an electrodeposition film.
  • the electrodeposition paint is a low-pollution paint, but regarding the phosphate treatment, phosphorus in the wastewater from the phosphate treatment process leads to eutrophication of the water quality and water pollution. It is urgently necessary to develop a new paint pretreatment method to replace the phosphate treatment, because of the cause of such problems and the shortage of phosphorus supply in the future.
  • An object of the present invention is to provide a novel chelate-forming resin capable of forming a strong metal chelate complex on a metal surface to prevent corrosion of a metal and capable of forming a film, and a method for producing the same. It is an object of the present invention to provide a novel metal surface treatment agent and a new anticorrosion paint using a chelating resin capable of forming a film that is non-polluting and has excellent anticorrosion properties.
  • Still another object of the present invention is to provide a novel method for forming an electrodeposition coating film, which has been subjected to a pre-coating treatment instead of the conventional phosphate treatment.
  • the present invention can form a film having about 0.2 to 3.5 mol of a chelate-forming group represented by the following general formula [1], [2], [3] or [4] per 1,000 g of a resin. It is intended to provide a chelating resin.
  • R 2 are the same or different, and are a hydrogen atom, a halogen atom, a nitro group, a nitroso group, a cyano group, a hydrocarbon group having 18 or less carbon atoms, and an alkoxyalkyl group having 12 or less carbon atoms. Is shown.
  • an object of the present invention is to provide a method for producing the above chelate-forming resin, wherein an addition reaction is carried out with a polymerizable double bond in a resin or compound having a heavy bond.
  • R 1 and R 2 have the same meaning as described above.
  • the present invention also provides a metal surface treatment agent and a corrosion preventive paint containing the above chelate-forming resin, and a chelate-forming resin composition obtained by blending the resin with a crosslinking agent.
  • the present invention relates to forming an electrodeposition coating film on a metal surface, and performing electrodeposition coating on a metal surface which has been subjected to a pre-coating treatment by bringing the metal surface treatment agent into contact with the metal surface.
  • An object of the present invention is to provide a method for forming an electrodeposition coating film.
  • the present inventor has proposed that a non-polluting surface treatment agent can be used instead of an inorganic surface treatment agent such as phosphate or chromic hydrochloric acid, and that the anticorrosion is superior to an epoxy resin or a fuanol resin.
  • the resin capable of forming a film has a specific amount of the above-mentioned specific chelate-forming group in which a nitrogen atom is bonded to an ortho position with respect to a phenolic hydroxyl group, so that a metal formed by chelation can be formed.
  • the binding energy of the steel exceeds the corrosion reaction energy.
  • the charge of the metal ion can be neutralized.
  • the coating of this resin shows excellent corrosion resistance.
  • the present invention has been completed based on these new findings.
  • the hydrocarbon group in 2 has 18 or less carbon atoms, preferably 5 or less carbon atoms, and includes an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and the like. Further, the alkoxyalkyl group in R 1 and R 2 is
  • alkyl group alkoxyalkyl group, cycloalkyl group, aralkyl group and aryl group in R 1 and R 2 of the chelate-forming group are shown below.
  • the alkyl group may be a straight-chain or branched-chain, for example, methyl, ethyl, ⁇ -propyl, isopropyl, ⁇ -butyl, n-hexyl, n-octyl, 2 —Ethylhexyl group, n— Dodecyl group and n—
  • unoctadecyl group and the like alkoxyalkyl groups such as 2-methoxethyl and 3-methoxypropyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl and 3-methylcyclyl 5-hexyl group; aralkyl group, for example, benzyl group, 4-methylbenzyl group, 4-isopropylbenzyl group, phenethyl group, etc .; For example, a phenyl group, a diphenyl group, a naphthyl group, a 4-methylphenyl group and the like can be mentioned.
  • Representative examples of the chelate-forming group represented by the above [1], [2], [3] or [4] include:
  • the chelate-forming group is a portion forming a stable 5-membered ring-type chelate complex of +2 or +3 metal ion with a nonionic intramolecular complex. is there.
  • the chelate complex to be formed is abbreviated as H 0 N H and modeled as follows.
  • three sets of chelate-forming groups are bonded to + trivalent metal ions, and two sets of chelate-forming groups are bonded to + divalent metal ions.
  • the charge of the metal ion forms a 5-membered chelate complex neutralized by the phenoxide ion.
  • the formed chelate complex is neutralized in charge and non-ionic, so that corrosion current does not easily flow against metal corrosion, and it is structurally stable because it has a 5-membered ring It is.
  • the chelate-forming resin of the present invention needs to have about 0.2 to 3.5 moles of the above chelate-forming group in 100 g of the resin, and may have 0.3 to 3.0 moles in 100 g of the resin. I like it.
  • the resin coating becomes three-dimensional when chelating is formed, and a strong chelating bond is formed, and the cross-linking density of the resin coating is increased. It will show anticorrosion properties.
  • the resin having a polymerizable double bond at a terminal or a side chain is not particularly limited, and various resins obtained by a known method can be used.
  • epoxy group-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and aryl glycidyl ether and other monomers.
  • the epoxy group of a resin having an epoxy group at the terminal or side chain such as a copolymer with a polymerizable monomer or various epoxy resins such as a bisphenol type, has a polymerizable group containing a carboxylic acid group such as (meth) acrylic acid.
  • hydroxyl groups in resins such as acrylic resins, polyester resins, alkyd resins, and epoxy resins that have hydroxyl groups are used for isocyanatoethyl (meta) acrylate
  • Introduction of polymerizable unsaturated groups by reacting polymerizable unsaturated group-containing isocynate compounds such as robininolefeninoleate and m-isopropinolenate-a, ⁇ -dimethylbenzyl isocyanate Can also be obtained.
  • This reaction can be carried out, for example, by reacting both in the presence of a tin-based catalyst such as dibutyltin octylate at 20 to 100 hours for about 1 to 10 hours.
  • the resin having a polymerizable double bond at the terminal or side chain obtained as described above can be reacted with the above ⁇ -aminophenols to form a resin represented by the general formula [1], [2], C33 Or, a chelating group represented by [4] is introduced.
  • Typical examples of 0-aminophenols represented by the general formulas [5], [6], [7] or [8] are ⁇ -aminophenol and 4-chloro-2-amino.
  • the addition reaction of o-aminophosphinols to the polymerizable double bond in the resin is carried out by reacting both at about 20 to 100 hours for about 1 to 24 hours, for example, in the presence of an acid catalyst. Can do it.
  • the reaction order in the method (a) is changed, and the chelating group represented by the general formula [1], [2], [3] or [4] and a hydroxyl group are used.
  • This is a method in which a reaction product having a first functional group such as carboxyl group or carboxyl group is first prepared, and the first functional group is reacted with a second functional group in a polymer to increase the molecular weight.
  • the compound having a chelate-forming group represented by the general formula [1], [2], [3] or [4] and a polymerizable double bond may be, for example, o-aminophenols.
  • the hydroxyl group in the addition product with a hydroxyl group-containing unsaturated compound such as 2-hydroxyhydryl (meth) acrylate is converted to isocyanatoethyl (meta) acrylate, m-isopropionyl olefenyl isocyanate.
  • the compound can be obtained by a method of reacting with a polymerizable double bond-containing mono-isocyanate compound such as m-isopropenyl-, a-dimethylbenzyl isocyanate.
  • a polymerizable double bond-containing mono-isocyanate compound such as m-isopropenyl-, a-dimethylbenzyl isocyanate.
  • the reaction between aminophenols and hydroxyl-containing unsaturated compounds can be carried out, for example, in the presence of an acid catalyst in an equimolar amount of about 20 to 100 for about 1 to 24 hours. This can be done by reacting.
  • the addition product thus obtained has a hydroxyl group, and the urethanation reaction of this with a polymerizable double bond-containing monoiso- nate compound is carried out, for example, in the presence of a tin-based catalyst so that both are equimolar.
  • the reaction can be carried out at about 20 to 100 for about 1 to 10
  • the compound having a chelate-forming group of the general formula [1], [2], [3] or [4] and a polymerizable double bond may be obtained by a method other than the above.
  • the method (c) another compound used for copolymerizing with a compound having a chelate-forming group of the general formula [1], [2], [3] or [4] and a polymerizable double bond is used.
  • the polymerizable unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Acrylic acid Hydroxyl-containing unsaturated monomers such as hydroxyalkyl esters and aryl alcohols; styrene, ⁇ -methyl Aromatic vinyl compounds such as styrene and vinyltoluene; dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and getylua Polymerizable unsaturated monomers having a secondary or tertiary amino group such as minopropionate (meta) acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid Acid-containing unsaturated monomers such as acid, maleic acid, and fumaric acid; vinyl acetate, (meth) acrylamide, (meth) acrylonitrile, N-methylol (meta) Monomers such as acrylamide butyl ether can be exemplified, and these can be used alone or in
  • the copolymerization of the above compound having a chelate-forming group and a polymerizable double bond with the other polymerizable unsaturated monomer can be carried out by a known copolymerization method. And preferably, by heating and reacting in the presence of an organic solvent.
  • a silane compound having a polymerizable double bond and an etherified silanol group is preferably a silane compound represented by the following general formula [9].
  • A represents an unsaturated hydrocarbon group or an unsaturated carbonylquinalkyl group
  • X represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, It represents an aryloxy group having from 8 to 8 carbon atoms or an alicyclic hydrocarbonoxy group having from 5 to 8 carbon atoms.
  • Y and Z are the same or different and each represents an alkoxyl group having 1 to 18 carbon atoms, an aryloxy group having 8 to 8 carbon atoms or an alicyclic hydrocarbon oxy group having 5 to 8 carbon atoms, and is the same as X It may be.
  • Preferred examples of the above A include vinyl group, aryl group, methacryloyloxyethyl group, acryloyloxyethyl group, methacryloyloxypropyl, and acrylyloxypropyl group. And the like.
  • an alkoxyl group having 1 to 18 carbon atoms an aryloxy group having 6 to 8 carbon atoms, a carbon atom Among the 5 to 8 alicyclic hydrocarbon groups, preferred are, for example, carbon atoms such as methoxy, ethoxy, propoxybutoxy, hexoxy, octoxy and methoxyxoxy groups. Examples thereof include 1 to 8 alkoxyl groups, phenoxy groups, and cyclohexyloxy groups.
  • hydrocarbon groups having 1 to 18 carbon atoms preferred are hydrocarbon groups having 1 to 18 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl. 6 to 6 alkyl groups; phenyl, methylphenyl, ethylphenyl, etc., 6 to 8 carbon atoms aryl groups; cyclopentyl, cyclohexyl, 5 to 8 carbon atoms alicyclic hydrocarbon groups .
  • silane compound represented by the above general formula [9] include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris ( ⁇ -propoxy) silane, allyl lime methoxy silane, ⁇ -acryloyloxysh Toxixylane, r-acryloyloxyprobilt limetoxysilane, armethacryloyloxy lip mouth, built-in rimethoxysilane, ⁇ -methacryloyloxypropyl (methyljetoxy) silane, armethacryloyloxypropyl ethoxylate, 5-metacryl Royloxyprovirt squirrel (n-butoxy) silane, Derivatives Cryloyloxyprobitris (isopropoxy) silane.
  • silane compounds having an etherified silanol group that can be partially co-condensed with the silane compound represented by the general formula [9] include two or more etherified silanol groups.
  • Silane compounds can be used, e.g., tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, ethyltrimethoxirane, dimethyl dimethoxysilane.
  • silane compounds such as diphenyldimethoxysilane, and partial cocondensates of these silane compounds.
  • reaction can be carried out in accordance with a method for condensing an etherified silane compound, and is generally carried out in the presence of an acid such as an organic acid such as acetic acid, an inorganic acid such as hydrochloric acid, and water, at a temperature from room temperature to a boiling point or lower, preferably 50 ° C or lower. It can be carried out by heating to ⁇ 90.
  • an acid such as an organic acid such as acetic acid, an inorganic acid such as hydrochloric acid, and water
  • the amount of water may be increased or decreased appropriately depending on the degree of condensation ⁇ 2
  • a silane compound or a resin having a polymerizable double bond and an etherified silanol group to an o-aminophenol
  • the compound represented by the general formula (1), (2), (3) or A silane compound or resin having a chelate-forming group [4] and an etherified silanol group is obtained.
  • the above addition reaction is usually carried out in the presence of an acid catalyst, for example, usually at about 2 C!
  • the reaction can be carried out at about 100 to 100 hours for about 1 to 24 hours.
  • the resin obtained by this method is included in the chelate-forming resin of the present invention.
  • the chelate-forming resin of the present invention can also be obtained by partially condensing the silane compound or resin obtained by the above addition reaction or partially cocondensing with the other silane compound having an etherified silanol group.
  • the partial condensation and the partial cocondensation can be performed in the same manner as in the partial (co) condensation method described above.
  • the chelate-forming resin of the present invention obtained by the method (d) has an etherified silanol group, and this group reacts with moisture in the air and is hydrolyzed to form a silanol group.
  • a so-called moisture hardening type can be formed by a crosslinking reaction.
  • the resin obtained by the method (a), (b) or (c) above also has a silanol etherified in the resin.
  • a group By introducing a group, it can be made to be a moisture-curing type.
  • etherified silanol groups into the resin for example, an alcoholic hydroxyl group is present in the resin, and a monoiso- nate compound having a silanol group etherified into the hydroxyl group is converted to, for example, a tin catalyst.
  • a method of reacting both at about 20 to 100 for about 1 to 10 hours in the presence of is available.
  • Representative examples of the above-mentioned monoisosilicate compound having an etherified silanol group include, for example, isocyanatoprovir trimethoxysilane, 7-iso cyanatoprovir triethoxysilane, and the like. Can be
  • the chelate-forming resin of the present invention may be a resin obtained by a method other than the above-mentioned methods (a) to (d) or these modification methods.
  • the chelate-forming resin of the present invention needs to have a film-forming ability, and preferably has a number average molecular weight of about 500 to 500,000, more preferably about 700 to 200,000. It is appropriate to be within. Further, the chelate-forming resin of the present invention needs to have about 0.2 to 3.5 mol of the above-mentioned chelate-forming group in 1,000 g of the resin, and more preferably 0.3 to 3.0 mol. It is preferred to have moles. In addition, the chelate-forming group is reduced in one resin molecule. It is preferable to have at least one, and more preferably 3 to 700.
  • the base resin of the chelate-forming resin of the present invention various resins can be used as described above. However, acrylic resin, epoxy resin, polyester resin, alkyd resin, Gay-containing resins are preferred o
  • the resin of the present invention may be used after being diluted with an organic solvent, or may be used after being made aqueous.
  • a resin may be dispersed or dissolved in water by introducing a basic group such as an amino group or an acid group such as a carboxyl group into the resin and neutralizing these groups. .
  • the amount of the basic group in the resin is adjusted, for example, so that the amine value becomes 30 to: L3O mg KOH g resin
  • the basic group may be neutralized with an acid, for example, an organic acid such as formic acid, dicarboxylic acid, propionic acid, or lactic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid.
  • an acid group such as a carboxyl group
  • the amount of the acid group is adjusted so that the acid value becomes, for example, 30 to 130 mg K0HZg resin, and the acid group is converted to an organic amine. It may be neutralized with a base such as ammonia.
  • the amino group introduced into the resin becomes a chelate-forming group. It may be based on minophenols, or may be based on both O-aminophenols and other amino group-containing compounds.
  • amino group-containing compounds other than aminofunol include aliphatic, alicyclic or aromatic monoaliphatic primary or secondary amines (these are epoxy Tertiary amino monoisosocyanate obtained by the reaction of tertiary amino alcohol with diisocyanate (which can react with hydroxyl groups in the resin) Reacts to introduce an amino group into the resin) and a polymerizable unsaturated monomer having a secondary or tertiary amino group (for example, the resin is obtained by copolymerization in the method (c)). An amino group may be introduced into the compound).
  • Examples of the above primary or secondary amines include, for example:
  • Primary monoamines such as methylamine, ethylamine, n- or iso-propylamine, monoethanolamine, ⁇ - or is0-propanolamine ;
  • the first type such as ethylenediamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylethylamine, dimethylaminopropylamine, etc.
  • a second-class polyamine such as ethylenediamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylethylamine, dimethylaminopropylamine, etc.
  • a second-class polyamine such as ethylenediamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, dimethylaminoethylethylamine, dimethylaminopropylamine, etc.
  • These primary or secondary amines may be reacted directly with the epoxy group when the resin has an epoxy group, but in general, the primary or secondary amines described above are the primary amines.
  • amine N-hydroxyalkyl secondary amide it is preliminarily combined with ketone, aldehyde or carboxylic acid, for example, in a range of 100 to 230. It is preferable to use a heat-reacted substance to denature to aldimin, ketimine, oxazoline or imidazoline, and use this.
  • the reaction of these primary, secondary and modified amines with epoxy groups in the resin can be carried out, for example, at a temperature of about 80 to about 200 at a temperature of about 2 to about 200. This can be done by heating for about 5 hours.
  • an amino group can also be introduced by adding a primary amine to the polymerizable unsaturated group.
  • the addition reaction is carried out in both cases, for example in the presence of an acid catalyst in about 20 to 100 to about 1 to 1
  • the reaction can be carried out for 24 hours.
  • a tertiary amino monoisocyanate is used as the amino group-containing compound, for example, it is reacted with an alcoholic hydroxyl group in a resin at a temperature of about 30 to 120 to infrared rays.
  • the reaction may be carried out until the absorption of the isocyanate group is completely eliminated by the absorption spectrum measurement.
  • a secondary or tertiary amine as part or all of another polymerizable unsaturated monomer copolymerized with a compound having a chelate-forming group and a polymerizable double bond represented by A polymerizable unsaturated monomer having a amino group may be used.
  • examples of the acid group introduced into the resin include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • an epoxy group is provided in the resin, and an excess molar amount of a polybasic acid having the above acid group is reacted with the epoxy group.
  • polybasic acids include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, succinic acid, glutaric acid, and adivine Acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) trimellitic acid, vilomeritic acid and the like.
  • another polymerizable unsaturated compound is copolymerized with a compound having a chelate-forming group and a polymerizable double bond.
  • a method of adding a thiocarboxylic acid having a thiol group is added to thiosalicylic acid, thioglycolic acid, or the like.
  • the resin of the present invention can be used in combination with a crosslinking agent that reacts with the reactive group by causing a reactive group such as a hydroxyl group other than the chelate-forming group in the resin.
  • a reactive group such as a hydroxyl group other than the chelate-forming group in the resin.
  • the crosslinking agent may be a known polyisocynate compound, a blocked polyisocynate compound, or an aminoblast resin, that is, urea, melamine, benzoguanamine, or the like.
  • Cross-linking can be carried out at room temperature or by heating using a formaldehyde condensate of the nitrogen-containing compound described above or a lower alkyl etherified product of this condensate (the alkyl group has 1 to 4 carbon atoms).
  • a formaldehyde condensate of the nitrogen-containing compound described above or a lower alkyl etherified product of this condensate the alkyl group has 1 to 4 carbon atoms.
  • an aminoblast resin ⁇ -toluenesulfonic acid, dodecylbenzenesulfonic acid,
  • a curing catalyst such as dinapthalphthalenesulfonic acid or an amine-neutralized product of these acids may be used in combination.
  • metal compounds such as tin octylate, dibutyltin dilaurate, dibutyltin oxide, dioctyl peroxide, and lead 2-ethylhexanoate are used. May be used in combination as a curing catalyst.
  • a hydroxyl group is present in the resin, and a compound in which one of the diisocyanate compounds is blocked is reacted with a part of the hydroxyl group, so that the blocked isocyanate is added to the resin.
  • a thio group a resin having a self-crosslinking property can be obtained.
  • a polymerizable unsaturated group is present in the resin of the present invention, and this resin is used in combination with a polymerizable unsaturated vinyl monomer, and a photopolymerization initiator is added as necessary.
  • a composition that can be cured by irradiation with an actinic ray such as an electron beam or an ultraviolet ray can be obtained.
  • the polymerizable unsaturated vinyl monomer conventionally known vinyl monomers can be used.
  • those exemplified as the other polymerizable unsaturated monomers in the method (c) described above, and ethylene glycol Examples include polyfunctional monomers such as coal di (meth) acrylate and trimethylolpropane tri (meth) acrylate.
  • the introduction of polymerizable unsaturated groups into the resin involves adding epoxy groups to the resin.
  • a method may be used in which a carboxyl group-containing polymerizable unsaturated compound is added thereto and added thereto.
  • the resin of the present invention can be either an organic solvent type or an aqueous type.
  • the resin alone or in combination with a crosslinking agent, a vinyl monomer, etc., and further, if necessary, a pigment, a surface conditioner, an oxidizing agent, or the like. It can be used as a metal surface treatment agent or anti-corrosion paint, etc., by incorporating an agent or the like.
  • This surface treatment agent contributes to corrosion prevention of the metal by forming a thin treatment agent layer on the metal surface.
  • These surface treatment agents and anti-corrosion paints are applied to the substrate by spray coating, brush coating, roll coating, dip coating, kaolin electrodeposition coating, anion electrodeposition coating, immersion automatic deposition, silk screen printing, etc.
  • the dry film thickness is preferably about 0.1 to 5 m, and when used as an anticorrosive paint, the dry film thickness is preferably about 1 to 50 // m.
  • the substrate to be applied include metals such as iron, zinc, copper, and aluminum, and those obtained by subjecting these metal surfaces to a surface treatment such as a phosphate treatment or a chromate treatment.
  • the resin of the present invention is a metal which generates +2 or +3 metal ions by corrosion of iron, zinc, copper, aluminum, etc. It can provide excellent anticorrosion properties and is pollution-free. For this reason, the resin of the present invention is extremely useful as a metal surface treating agent or an anticorrosion paint.
  • the method for forming an electrodeposition coating film of the present invention is a method for performing electrodeposition coating on a metal surface that has been subjected to pre-coating treatment by bringing a metal surface treatment agent containing the chelate-forming resin of the present invention into contact with the metal surface. is there.
  • the metal surface treatment agent which is a pretreatment agent for coating in the method for forming an electrodeposition coating film of the present invention, may be either the organic solvent type or the aqueous type containing the chelate-forming resin, Containing various optional ingredients, such as an agent.
  • the coating pretreatment agent used in the present invention may further contain, if necessary, an oxidizing agent such as sodium chlorate and nitrous acid; and an etching aid such as ethylenediamine tracetate. Good.
  • concentration of the chelate-forming resin in the pretreatment agent for coating is preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.5 to 5% by weight.
  • the coating pretreatment agent is brought into contact with the metal material surface by dipping, spraying, roll coating, brush coating, spin coating, squeezing, etc. to form a film.
  • pre-treatment for electrodeposition coating is performed on the metal surface.
  • the metal surfaces to be pre-treated include surfaces of metals such as iron, zinc, mesh, and aluminum, and these metal surfaces are subjected to a chemical conversion treatment such as a phosphate treatment, a chromate treatment, a boehmite treatment, and an anodizing treatment. Surface and the like.
  • the metal surface subjected to the above-mentioned pre-coating treatment is subjected to electrodeposition coating.
  • the electrodeposition paint used for this electrodeposition coating may be either a Kachion type or an anion type, and is an electrodeposition coating used in the field of electrodeposition coating.
  • cationic electrodeposition coatings include, for example, polyamine resins represented by amine-added epoxy resins, for example,
  • the polyepoxide compound used for the production of the above polyamine resin is a compound having two or more epoxy groups in one molecule, and is generally at least 200, preferably 400 to 400. Suitable are those having a number average molecular weight in the range of 800 to 200, more preferably those obtained by the reaction of a polyphenol compound with epichlorohydrin. .
  • polyphenol compound examples include bis (4-hydroxyphenyl) -1,2,2-propane, 4,4′-dihydroxybenzophenone, and bis (4-hydroxybenzene).
  • the polyepoxide compounds include polyols, polyether polyols, polyester polyols, and polyamide amides. • It may be partially reacted with carboxylic acid, polycarboxylic acid, polyisocyanate compound, etc., and it is also obtained by graft polymerization of e-force prolactone, acryl monomer, etc. It may be.
  • an amino group-containing acrylic resin or a nonionic acrylic resin having excellent weather resistance is used as a resin component. It is convenient to use the resin alone or in combination with the above-mentioned amine-added epoxy resin.
  • the aforementioned amine-added epoxy resin can be cured using a polyisocyanate compound blocked with an alcohol or the like, if necessary.
  • an amine-added epoxy resin that can be cured without using a blocked isocyanate compound.
  • a hydroxyalkyl carbamate group is introduced into a polyepoxide material.
  • Resins for example, see JP-A-59-155470
  • resins of a type that can be cured by transesterification for example, see JP-A-55-80436
  • Preparation of the above-mentioned cation-based aqueous solution or aqueous dispersion of the cation electrodeposition coating resin is usually carried out by formic acid, acetic acid, It can be carried out by neutralizing with a water-soluble organic acid such as lactic acid and solubilizing and dispersing in water.
  • anionic electrodeposition paints include, for example, a polycarboxylic acid resin, for example, a saturated or unsaturated alkyd resin having a carboxyl group, an oil-modified product thereof, and an acrylic resin having a carboxyl group. And those containing maleated polybutadiene-based resin as a resin component.
  • This polycarboxylic acid resin can be cured by using a blocked polyisocyanate compound or an amino resin such as a melamine resin or a urea resin, if necessary.
  • the preparation of the anionic aqueous solution or aqueous dispersion of the resin for anionic electrodeposition coating is usually carried out by neutralizing the resin with a basic substance, that is, an organic amine or ammonia, and not dissolving the resin in water. It can be carried out by dispersing in water.
  • an aqueous coating solution or dispersion of the above resin and, if necessary, ordinary coating additives such as coloring pigments such as titanium white, carbon black, red iron oxide, etc. , Chromium pigments such as strontium chromate, zinc chromate, basic gay acid, etc .; anti-pigment pigments such as strontium chromate, zinc chromate, etc .; Lead pigments such as lead; other additives can be added You.
  • additives include, for example, dispersing aids (nonionic surfactants, etc.); anti-cissing agents for coated surfaces (acrylic resins, fluororesins, silicon resins, etc.); curing accelerators (eg, lead, bismuth, etc.) , Tin and other metal salts); organic polymer fine particles (acrylic resin, etc.) with a particle size of about 0.01 to 0.5; / m for the purpose of improving the coating properties on the end face of the material, etc. Are listed.
  • the coating surface of the coating pretreatment agent is brought into contact with the metal surface by dipping or the like to form a coating of the coating pretreatment agent on the metal surface in a dry film thickness of about 0.01 to 5 ⁇ . m, preferably 0.1 to 3 jKin, and, if necessary, curing by heating or the like, and then applying the pre-coating metal surface to the cationic or anion-based metal surface.
  • the electrodeposition paint is applied by electrodeposition.
  • the coating pretreatment agent is cured, it may be cured before the electrodeposition coating, or may be cured simultaneously with the electrodeposition coating after the electrodeposition coating.
  • cation electrodeposition coating on a metal surface which has been subjected to the above-mentioned coating pretreatment is diluted with deionized water or the like so that the solid content concentration of the cationic electrodeposition coating is about 5 to 40% by weight.
  • Cathode electrodeposition coating conditions are not particularly limited, but generally, bath temperature: 15 to 35 (preferably 20 to 30), voltage: 100 to 400 V (preferably Or 200 to 300 V), current density: 0.01 to 3 AZdo ⁇ , energization time: 30 seconds to 10 minutes, pole area ratio (A / C): 61 to: L / 6, gap Distance: 10 to 100 cm, preferably electrodeposited with stirring.
  • the thickness (dry state) of the electrodeposited coating film formed is in the range of 5 to 70 / zm, preferably 10 to 50 wm.
  • the formed electrodeposition coating film may be omitted from the water washing treatment, or may be washed with deionized water or reverse osmosis membrane filtrate or the like, and then at a temperature equal to or higher than the curing start temperature of the electrodeposition coating material, preferably from 100 to At 250, more preferably by heating to 150-200 C, it can be cured.
  • the anion electrodeposition coating on a metal surface which has been subjected to the above-mentioned coating pretreatment is diluted with dewatering water or the like so that the solid content concentration of the anion electrodeposition coating is 5 to 40% by weight. It can be carried out using an electrodeposition bath in which H is adjusted in the range of 7 to 9.
  • Methods and apparatuses for performing anion electrodeposition coating include the conventional methods and apparatuses used in anion electrodeposition coating. Six known methods and devices can be used.
  • the conditions of the anion electrodeposition coating are not particularly limited, but generally, a direct current is applied at a voltage of 15 to 300 for 30 to 300 seconds.
  • the thickness (dry state) of the electrodeposited coating film formed is in the range of 3 to 70 m, preferably 5 to 50 m.
  • the electrodeposition coating film is subjected to a water washing treatment or the water washing treatment is omitted, and the temperature is equal to or higher than the curing start temperature of the electrodeposition paint, preferably 100 to 250, and more preferably 150 It can be cured by heating to about 200 ° C.
  • the chelating group of the chelating resin in the coating pretreatment agent has an amino group, and the coating pretreatment agent is used from the viewpoint of safety and health. It is preferable to use an aqueous type obtained by neutralizing the hydroxyl group, and it is more preferable to perform cationic electrodeposition from the viewpoint of the corrosion prevention of the electrodeposition coating film itself.
  • the electrodeposition coating material obtained by the coating film forming method of the present invention can be used as it is, or a paint may be applied thereon.
  • the coating system is not particularly limited, and examples thereof include an electrodeposition coating material and a top coat, and a primer coated with a middle coat, a chipping primer, a stone guard primer and the like during this time.
  • a novel coating pretreatment agent containing a chelating resin having a specific chelating group derived from o-aminophenols is used.
  • the chelate-forming group of the resin in the pre-treated film can form a stable nonionic intramolecular complex type 5-membered ring chelate complex with a +2 or +3 metal ion, Or, excellent corrosion resistance can be imparted to metal surfaces such as iron, zinc, copper, and aluminum which generate + trivalent metal ions.
  • the pre-coating treatment performed in the present invention has an electrodeposition characteristic that is equal to or more than that of the conventional zinc phosphate treatment, and can prevent the pre-coating treatment layer from being deteriorated during the electrodeposition coating. It can be made pollution-free without problems of water contamination due to phosphorus in the phosphate treatment, and can be used in combination with electrodeposition coating to achieve surface treatment-low paint pollution and high corrosion protection.
  • Example 1 8 In a flask, mix 109 parts of o-aminophenol, 58 parts of N, N-dimethylformamide and 0.1 part of hydroquinone, and heat to 70 with stirring to remove 0-aminophenol. Dissolved and kept at 70. A mixture of 72 parts of acrylic acid and 2.3 parts of copper acetate as an addition reaction catalyst was added dropwise over 2 hours, and after completion of the dropwise addition, the temperature was raised to 90 and reacted at 90 to 3 hours. Thus, an adduct solution was obtained.
  • a chelate-forming resin solution having a solid content of 50%.
  • the chelating group concentration of this resin was 1.38 mol Zlk (resin solids).
  • the number average molecular weight of this resin was about 12,000.
  • Denacol EX 521 (Nagase Kasei Co., Ltd., polyol polyglycidyl ether, number average molecular weight about 1200, epoxy equivalent about 200), methyl isoptyl ketone 118 parts, acrylic Mix 76 parts of acid, 2.5 parts of tetraethylammonium bromide and 0.3 part of hydroquinone, and heat at 110 for 3 hours to react epoxy group with carboxy group.
  • a resin solution having a polymerizable unsaturated group and a hydroxyl group was obtained.
  • ⁇ 249 parts of the above-obtained partially-blocked polyisocyanate solution were blended, and the resin was reacted at 70 for 3 hours.
  • a block isocyanate group was introduced therein. To this were further added 91 parts of o-aminophenol, 37.5 parts of oxalic acid, 17.5 parts of diethanolamine and 43 parts of isopropanol, and reacted at 70 for 3 hours. A 50% chelate-forming resin solution was obtained. The chelating group concentration of this resin is 1.54 mol 1 kg
  • Example 2 35 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 1 was mixed with 1 part of Symmar M 551, 24 parts of methyl isobutyl ketone, 28 parts of isopropanol and 2 parts of water to obtain a coating composition B.
  • Symmar M 551, 24 parts of methyl isobutyl ketone, 28 parts of isopropanol and 2 parts of water 35 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 1 was mixed with 1 part of Symmar M 551, 24 parts of methyl isobutyl ketone, 28 parts of isopropanol and 2 parts of water to obtain a coating composition B.
  • Symmar M 551 24 parts of methyl isobutyl ketone, 28 parts of isopropanol and 2 parts of water
  • Example 10 In 4 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 2, 0.7 parts of Sumimal M55, 60 parts of methyl isobutyl ketone, 25 parts of ethanol, 9.8 parts of water, and 0.5 part of citric acid Were mixed to obtain a surface treatment composition C.
  • Example 10 In 4 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 2, 0.7 parts of Sumimal M55, 60 parts of methyl isobutyl ketone, 25 parts of ethanol, 9.8 parts of water, and 0.5 part of citric acid Were mixed to obtain a surface treatment composition C.
  • Example 10 In 4 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 2, 0.7 parts of Sumimal M55, 60 parts of methyl isobutyl ketone, 25 parts of ethanol, 9.8 parts of water, and 0.5 part of citric acid Were mixed to obtain a surface treatment composition C.
  • Example 10 In 4 parts
  • Example 2 35 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 2 was mixed with 11 parts of Sumimar M55, 24 parts of methyl isobutyl ketone, 28 parts of isopropanol, and 2 parts of water to obtain a coating composition D. .
  • Example 3 To 10 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 3, 60 parts of methyl isobutyl ketone, 20 parts of toluene, 8 parts of ethanol and 2 parts of a 1% formic acid aqueous solution are mixed. Thus, a surface treatment composition E was obtained.
  • Example 3 To 50 parts of the chelating resin solution having a solid content of 50% obtained in Example 3, 20 parts of methyl isobutyl ketone, 20 parts of isobutanol, 9 parts of ethanol, and a 0.5% aqueous solution of citric acid One part was blended to obtain a coating composition F.
  • Example 6 The solid obtained in Example 6 was stirred under stirring in a mixture of 79.5 parts of a 7% aqueous solution of formic acid and 0.5 part of sodium chlorate. 20 parts of a chelate-forming resin solution of 50% by weight were gradually added and mixed uniformly to obtain an automatic deposition type surface treatment composition K, Example 18.
  • Example 6 40 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 6 was gradually added to 60 parts of a 0.2% formic acid aqueous solution with stirring, and the mixture was uniformly mixed. I got Test examples 1 to 6
  • Each of the surface treatment compositions A, C, E, G, I, and K obtained in Examples 7, 9, 11, 13, 15, and 17 was dried on various materials as shown in Table 1. It was applied to a thickness of 0 and air-dried.
  • Test Example 6 using the surface treatment composition K, the material was immersed in the composition K, and was subjected to automatic deposition to form a surface treatment film.
  • each surface treatment composition was applied by Barco overnight.
  • a top coat was applied on the obtained surface-treated film and dried to form a top coat.
  • an epoxy-melamine paint (abbreviated as “EPZMEJ” in Table 1) was applied to a dry film thickness of about 40 m, and was applied at 140 for 30 minutes.
  • the urethane-based white enamel paint (abbreviated as "urethane” in Table 1) had a dry film thickness. It was applied to a thickness of 20 zm and dried at room temperature for 5 days.
  • an epoxy / polyamine-based white enamel paint (abbreviated as ⁇ ⁇ ⁇ in Table 1) was applied to a dry film thickness of 50 m and dried at room temperature for one day. Thereafter, a white enamel paint of a polyol / polyisocyanate type (abbreviated as “POZP IJ” in Table 1) was applied thereon so as to have a dry film thickness of 25, and dried at room temperature for 4 days.
  • POZP IJ a white enamel paint of a polyol / poly
  • Each of the chelate-forming coating compositions B, D, F, H, J, and L obtained in Examples 8, 10, 12, 14, 16, and 18 was prepared using various materials under the conditions shown in Table 2. Coated on top and dried. In Test Examples 7, 8, and 10, a top coat was applied on the obtained coating No. 1 and dried to form a top coat. In Test Examples 7 and 8, an acrylic-melamin-based white enamel paint (abbreviated as “acryl J” in Table 1) was used as the top coat, and the dry film thickness was 20 ⁇ m. It was baked for 30 minutes at 140. In Test Example 10, the same paint as the urethane-based white enamel paint used in Test Example 4 was used as the top coat, and the dry film thickness was 20%. m and dried at room temperature for 5 days. Comparative test examples 1 to 3
  • the acrylic-melamine white enamel paint used in Test Example 7 was applied to various materials so that the dry film thickness became 20 zm, and baked at 140 ° C for 30 minutes.
  • the epoxy-polyamine white enamel paint used in Test Example 5 was applied to various materials to a dry film thickness of 30 m, dried at room temperature for one day, and then placed on Test Example 7
  • the acrylic-melanic white enamel paint used in (1) was applied to a dry film thickness of 20 / m and baked at 14 CTC for 30 minutes.
  • Salt spray test (S ST): A cross-cut was made on the coated plate: The test was carried out according to TIS Z 2371. The salt water spraying time was 1000 hours.
  • FCT Fatigue cracking resistance test
  • Example 2 55 parts of 2-amino-1-naphthol was used instead of 43 parts of 5-methyl-2-aminophenol, and the amount of methylisobutyl ketone was changed from 88.9 parts to 110 parts. In the same manner as in Example 2 except that the amount was changed to 9 parts, a chelate-forming resin solution having a solid content of 50% was obtained. The concentration of the chelating groups in this resin was 1.92 moles 1 kg (resin solids). The number average molecular weight of this resin was about 45,000.
  • Another flask was mixed with 50 parts of methyl isobutyl ketone, and heated and maintained at 85.
  • 50 parts of ethyl methacrylate isocyanate, 30 parts of isobutyl acrylate, 20 parts of styrene and 2,2'-azobisisobutyl ester The mixture of lonitrile (2 parts) was added dropwise over 2 hours under nitrogen gas flow. After the addition, the mixture was kept at the same temperature for 2 hours to obtain an isocyanate group-containing acrylic resin solution.
  • 108 parts of the hydroxyl-containing chelate compound solution obtained above was added thereto, and the mixture was reacted at 70 at room temperature for 2 hours.
  • a chelate-forming resin solution having a solid content of 50%.
  • the concentration of the chelating groups in this resin is 1. It was 61 mol Z lkg (resin solids).
  • the number average molecular weight of this resin was about 10,000.
  • Example 19 35 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 19 were mixed with 1 part of Sumimal M 55 11, 24 parts of methyl isobutyl ketone, 28 parts of isopropanol and 2 parts of water to obtain a coating composition B ′. Obtained.
  • Example 27 In 4 parts of the chelating resin solution having a solid content of 50% obtained in Example 20, 0.7 parts of Sumimal M 55, 60 parts of methyl isobutyl ketone, 25 parts of ethanol, 9.8 parts of water, and 0.5 part of citric acid And a surface treatment composition C ′ was obtained by blending the following parts ⁇ Example 28>
  • Example 20 35 parts of the chelating resin solution having a solid content of 50% obtained in Example 20 were mixed with 5 parts of Sumimar M 55 1 1 part, methyl isobutyl ketone 24 parts, isopropanol 28 parts and water 2 parts to obtain a coating composition D ′. I got
  • Example 21 52.5 parts of methyl isobutyl ketone, 20 parts of toluene, 8 parts of ethanol and 2 parts of a 1% aqueous solution of anaerobic acid were mixed with 12.5 parts of the chelate-forming resin solution having a solid content of 40% obtained in 1 Thus, a surface treatment composition E 'was obtained.
  • Example 21 50 parts of the chelating resin solution having a solid content of 50% obtained in Example 21 were mixed with 20 parts of methyl isobutyl ketone, 20 parts of isobutanol, 9 parts of ethanol and 1 part of a 0.5% aqueous solution of citric acid to prepare a coating composition.
  • the thing F ' was obtained.
  • Example 32 8.5 parts of the chelate-forming resin solution having a solid content of 60% obtained in Example 22 was mixed with 1.2 parts of isophorone diisocyanate, A surface treatment composition G ′ was obtained by mixing 40 parts of methylisobutyl ketone, 10 parts of toluene and 40 parts of butyl acetate.
  • Example 32 8.5 parts of the chelate-forming resin solution having a solid content of 60% obtained in Example 22 was mixed with 1.2 parts of isophorone diisocyanate, A surface treatment composition G ′ was obtained by mixing 40 parts of methylisobutyl ketone, 10 parts of toluene and 40 parts of butyl acetate.
  • Example 22 To 34 parts of the chelating resin solution having a solid content of 60% obtained in Example 22, 5 parts of isophorone diisocynate, 30 parts of methyl isobutyl ketone, 20 parts of toluene, and 10 parts of butyric acid were mixed. A coating composition H ′ was obtained.
  • Example 23 10 parts of the chelating resin solution having a solid content of 50% obtained in Example 23 were mixed with 70 parts of isobutyl alcohol, 5 parts of ethanol and 15 parts of toluene to obtain a surface treatment composition I ′.
  • Example 3 5 105 parts of the white pigment paste obtained above, 100 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 23, and 100 parts of the moisture-curable acrylic resin solution obtained above 94 parts, ethanol 50 parts, methyl isobutyl ketone 100 parts and toluene 51 parts were uniformly mixed to obtain a coating composition J ′.
  • Example 3 5 105 parts of the white pigment paste obtained above, 100 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 23, and 100 parts of the moisture-curable acrylic resin solution obtained above 94 parts, ethanol 50 parts, methyl isobutyl ketone 100 parts and toluene 51 parts were uniformly mixed to obtain a coating composition J ′.
  • Example 3 5 105 parts of the white pigment paste obtained above, 100 parts of the chelate-forming resin solution having a solid content of 50% obtained in Example 23, and 100 parts of the moisture-curable acrylic resin solution obtained above 94 parts, ethanol 50 parts, methyl isobut
  • Example 24 Under stirring, 40 parts of a chelating resin solution having a solid content of 50% obtained in Example 24 was gradually added to 60 parts of a 0.2% formic acid aqueous solution with stirring, and mixed uniformly. Thus, a coating composition L ′ was obtained.
  • Test Example 13 L 8
  • Each of the surface treatment compositions A ′,, E ′, G ′, I ′ and ⁇ ′ obtained in Examples 25, 27, 29, 31, 33 and 35 was placed on various cord materials as shown in Table 3. The coating was applied to a dry film thickness of 0.5 m and air-dried.
  • Test Example 18 using the surface treatment composition the cord material was immersed in the composition K ′, and the surface treatment film was formed by automatic precipitation.
  • each surface treatment composition was applied using a bar coater.
  • a top coat was applied on the obtained surface-treated film and dried to form a top coat.
  • an epoxy-melamine paint (abbreviated as “EPZMEJ” in Table 3) was applied so that the dry film thickness was about 4 O ⁇ m.
  • a urethane-based white enamel paint (abbreviated as “urethane” in Table 3) was applied so that the dry film thickness became 20 m, and the room temperature was changed to room temperature. For 5 days.
  • an epoxy ⁇ polyamine-based white enamel paint (abbreviated as “EPZPA” in Table 3) was applied to a dry film thickness of 50 m and dried at room temperature for one day.
  • a polori polyisocyanate-based white enamel paint (“P0” in Table 3) Abbreviated as ZP IJ. ) was applied to a dry thickness of 25 and dried at room temperature for 4 days.
  • Each of the chelating coating compositions B ′, D ′, F ′, H ′, J ′ and L ′ obtained in Examples 26, 28, 30, 32, 34 and 36 is shown in Table 4. It was applied and dried on various materials under the conditions shown below. In Test Examples 19, 20, and 22, a topcoat was applied on the obtained coating and dried to form a topcoat. In Test Examples 19 and 20, an acrylic-melanin-based white enamel paint (abbreviated as “acryl” in Table 4) was used as the top coat, and the dry thickness was 2%. It was painted so as to be 0 im and baked at 140 for 30 minutes.
  • acryl acrylic-melanin-based white enamel paint
  • Test Example 22 the same paint as the urethane-based white enamel paint used in Test Example 16 was used as the top coat, and the paint was applied to a dry film thickness of 20 and dried at room temperature for 5 days. .
  • Example of the method for forming an electrodeposition coating film of the present invention Example of production of pretreatment liquid
  • Example 2 20 parts of a chelating resin solution having a solid content of 50% obtained in Example 2 was mixed with 600 parts of ethylene glycol monoethyl ether and 380 parts of deionized water to prepare a treatment liquid (1).
  • the flask was mixed with 32 parts of ⁇ -butyl alcohol, 1 part of tetraethylammonium bromide, and 18 parts of acrylic acid, and heated to 110 under air blowing, and maintained at the same temperature.
  • 125 parts of the resin solution (A) obtained in Example 2 was added dropwise over 1 hour, and after completion of the addition, the temperature was maintained for another 2 hours, and 14 parts of phthalic anhydride was added thereto. And kept at 110 for 2 hours to obtain an adduct solution having a polymerizable unsaturated group and a carboxy group.
  • the adduct solution was cooled to 50, and 39.8 parts of 2-amino-1-naphthol and 24.4 parts of dimethylformamide were mixed therein and reacted at 50 for 12 hours. 89.4 parts of methyl isobutyl ketone was added to obtain a chelating resin solution having a solid content of 50%.
  • the chelate-forming group concentration of this resin was 1.46 mol Zlkg (resin solids).
  • the number average molecular weight of this spore was about 430000.
  • the mixture was added dropwise over a period of time, and after completion of the addition, the mixture was maintained at the same temperature for 3 hours to obtain an adduct solution having a polymerizable unsaturated group having a solid content of 80%.
  • the resin acid value of this solution was 0.1 or less.
  • Benzine was added to 25 parts of the obtained chelating resin solution. Add 0.6 parts of alcohol and 40 parts of deionized water and uniformly mix the mixture. 890.2 parts of deionized water, 11.4 parts of a 10% aqueous formic acid solution and 34 parts of a 0.2% aqueous nitrous acid solution 33. The solution was dropped into 4 parts of the mixed solution and mixed uniformly to prepare a treatment solution (4).
  • a flask was mixed with 72 parts of acrylic acid, 2 parts of tetraethylammonium bromide, 0.3 parts of hydroquinone and 31.7 parts of methylisobutyl ketone, and heated and maintained at 110.
  • treatment film layers were formed on the following various materials by various methods.
  • Example 37 is a bar coater painting, air-drying and water-washing, In Example 38, Bako overnight coating was performed at 140 for X20 minutes and baked.
  • Example 39 is a dip coating, air drying and water washing
  • Example 40 is an automatic precipitation method by immersion, washing with water and air-drying
  • Example 41 is a coating method for removing excess processing liquid by centrifugal force after applying the processing liquid, and coating with air-drying and washing with air.
  • Example 42 was carried out by baking for 20 minutes in an automatic precipitation method by immersion, washing with water at 170 ° C, and washing for 170 minutes.
  • electrodeposition coating was performed on various materials on which the treated film layers were formed.
  • the electrodeposition coating conditions were as follows.
  • Electron No. 9410 gray manufactured by Kansai Paint Co., Ltd., cationic electrodeposition paint, epoxy polyamine resin
  • a block polyisocyanate-based gray paint, “Cation-1J” is used in Tables 5 and 6, and the applied film has a film thickness of 20 in at an applied voltage of 250 V. After the electrodeposition coating, the electrodeposition coating was washed with water, and then baked at 170 for 30 minutes to obtain an electrodeposition coating.
  • Electron N 0.70100 gray (manufactured by Kansai Paint Co., Ltd., anion-type electrodeposition paint, maleated polybutadiene resin-based gray paint, and Table 5) Abbreviated as "One Anion 2". ) was applied at an applied voltage of 200 V so as to have a thickness of 20 #m. After the electrodeposition coating, it was washed with water, and baked at 160 at 30 minutes to obtain an electrodeposition coated plate.
  • a zinc phosphate-treated plate treated with Palbond 300 was used, and electrodeposition coating was applied on it using the same method as in Example 37. .
  • the material was not subjected to the chelate-forming surface treatment, and was subjected to Kachion electrodeposition coating in the same manner as in Example 37 without any treatment.
  • Example 3 Regarding the electrodeposited coated plates obtained in 7 to 4 2 and Comparative Examples 1 to 3, the finished appearance, salt water spray resistance, and shot water immersion performance We tried welding on the street resistance. Table 5 shows the test results.
  • Finish appearance Visually observe the surface of the electrodeposited plate, and evaluate for bumps, dents, and smoothness. A is good, A is practically acceptable, B is slightly defective skin, and C is defective.
  • Saltwater spray resistance A crosscut was placed on an electrodeposition coated plate, and a test was performed in accordance with JIS Z2371. The salt spray time was 240 hours. Adhere the cellophane adhesive tape to the cross-cut part of the coated plate after the test welding, and rapidly peel off the adhesive. Obtain the maximum width of the cut and spout width on one side of the cross-cut part.
  • Warm salt water immersion resistance Put a cross cut on the electrodeposited coated plate, immerse in a 5% saline solution at 50 for 240 hours, pull up the coated plate, air-dry, and apply cellophane adhesive tape to the cross cut part. Closely contact and peel off sharply. Obtain the maximum width of the chip width and emission width on one side of the cross cut part.
  • Quenching resistance DuPont type under ambient atmosphere at 20 in accordance with JISK5400.0.3.2 (1900) Conduct a street test.
  • the weight is 500 g and the diameter of the tip of the heart is 1 to 2 inches. It shows the maximum falling weight height that does not damage the coating film. The maximum value is 50 cm.
  • Phosphorous acid Salt spray resistance (>> ») 0 0 0 0 0 0 0 0 0 0
  • Electrodeposition coating type * Thin-1 -1 Thion-1 -1 Thion-1 Cation-1 1 Thion-1 cation-1 Electrode 200V 21 20 20 21 20 21 Deposition Maximum electrodeposition film Thickness (m) 250V 25 25 26 25 25 24 26 Special 300V 28 29 29 29 28 30 Coulomb yield (mgZC) 32 32 32 32 32 33

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PCT/JP1992/000113 1991-02-05 1992-02-05 Film-forming chelating resin, production thereof, use thereof, and formation of electrodeposition coating WO1992013902A1 (en)

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US07/930,524 US5342901A (en) 1991-02-05 1992-02-05 Film-formable, chelate-forming resin, process for preparation thereof, use thereof and method for forming electrophoretic coating
DE4290288A DE4290288C2 (de) 1991-02-05 1992-02-05 Zu einem Film formbares, chelatbildendes Harz, Verfahren zur Herstellung desselben, Verwendung desselben und Verfahren zur Bildung eines elektrophoretischen Überzugs

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JP3/102182 1991-02-05
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JP3/42475 1991-02-13
JP3/35935 1991-03-01
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005099A1 (en) * 1997-07-21 1999-02-04 Commonwealth Scientific And Industrial Research Organisation Synthesis of dithioester chain transfer agents and use of bis(thioacyl) disulfides or dithioesters as chain transfer agents
CN114096581A (zh) * 2019-07-15 2022-02-25 凯密特尔有限责任公司 用于金属预处理的组合物和方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS592309B2 (ja) * 1976-06-16 1984-01-18 大日本塗料株式会社 キレ−ト結合性一液型塗料組成物
JPS6121575B2 (enrdf_load_stackoverflow) * 1982-07-15 1986-05-28 Shoji Yamada

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS592309B2 (ja) * 1976-06-16 1984-01-18 大日本塗料株式会社 キレ−ト結合性一液型塗料組成物
JPS6121575B2 (enrdf_load_stackoverflow) * 1982-07-15 1986-05-28 Shoji Yamada

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005099A1 (en) * 1997-07-21 1999-02-04 Commonwealth Scientific And Industrial Research Organisation Synthesis of dithioester chain transfer agents and use of bis(thioacyl) disulfides or dithioesters as chain transfer agents
US6512081B1 (en) 1997-07-21 2003-01-28 E.I. Dupont Nemours And Company Synthesis of dithioester chain transfer agents and use of bis(thioacyl) disulfides or dithioesters as chain transfer agents
CN114096581A (zh) * 2019-07-15 2022-02-25 凯密特尔有限责任公司 用于金属预处理的组合物和方法

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