JP2019111488A - Anticorrosion coating method for rust surface - Google Patents

Abstract

To provide an anticorrosive coating method using a simple surface treatment method to a rust surface.SOLUTION: An anticorrosive coating method for a rust surface includes a surface treatment step (1) for performing surface treatment of the rust surface by coating surface treatment liquid (A) containing water and an organic solvent (a1) in which the amount of the organic solvent (a1) occupied in the whole treatment liquid is in the range of 0.1-65 mass%, on the rust surface with a coating amount in the range of 50-550 g/m, so as to be impregnated thereinto, and a primer coating step (2) for coating a water-soluble anticorrosive paint (B) on a surface treatment part obtained in the step (1).SELECTED DRAWING: None

Description

  The present invention relates to an anticorrosion coating method suitable for rusty surfaces.

  Steel materials are widely used in various fields such as offshore structures, harbor facilities, ships, buildings, civil engineering structures, automobiles, etc., but they have a problem of corrosion when exposed to the natural environment. Anticorrosion coating is performed as a method of preventing or suppressing corrosion.

  In recent years, steel structures such as steel bridges, plants, steel towers, oil facilities, etc. have reached a period of aging and need to be repainted.

  Generally, in order to repaint a steel structure, it is important to treat the surface prior to painting, and the accuracy thereof affects the life of the coating. Specifically, examples of the surface treatment include the removal of rusted portions of rusted portions of steel structures, the roughening of the surface of the old coating, and the removal of a coating that has become brittle due to the loss of antirust effect. The degree of surface treatment is called "Keren", and it is classified from grade 1 to type 3 kelen depending on the grade, and the surface treatment is performed according to the treatment method according to the grade. Classification of the grade of kelen is not clearly defined, but kind 1 kelen means full-scale surface treatment which completely removes rust and coating film and cleans the steel surface, and three kinds of kelen are active film Is a simple surface treatment that removes rust and deteriorated coating, leaving two kinds of keren in between.

  And, in order to carry out the surface treatment to 1 type of kelen grade which is regarded as ideal in the repair coating of a steel structure, it is necessary to carry out a blasting technique such as sand blasting or shot blasting wherein abrasive particles are blown with compressed air. Such a blasting method has the problems that both machine noise and operation noise, and labor and time spent by the painter are large.

  In addition, when 1 type of kelen is adopted for the surface treatment, it is said that 60 to 70% of the cost required for the whole of the refinishing work is cost for blasting process and industrial waste treatment, and 2 types of keren or 3 types of keren There has been a need for an anticorrosion coating method that can exhibit long-term corrosion protection even with a simple surface treatment.

  As such a measure, Patent Document 1 proposes a method for forming a rust surface anticorrosive film, in which an epoxy resin paint containing a silane coupling agent is applied to a metal surface having a rust layer. According to the method described in Patent Document 1, the silane coupling agent that has been affected by the moisture in the rust layer fixes the rust layer and the metal surface, and is provided thereon even if the rust remains on the metal surface Although the anticorrosive coating can protect the substrate, sufficient quality has not yet been obtained.

  In Patent Document 2, an organic or inorganic zinc-rich paint is applied to a rusted steel surface to a dry film thickness of 15 to 30 μm, and an epoxy resin is formed on the obtained primary antirust coating film. Disclosed is an anticorrosion method for a rust surface to be coated with a paint, which can suppress the progress of rust by the sacrificial anodic action of zinc by the anticorrosion method and can simplify the surface treatment step in the anticorrosion coating of the steel surface on which rust is generated. It is done. However, in Patent Document 2, although it is a rust surface, it is a relatively careful treatment to remove all layered rust and hump rust, and is intended for repainting of a structure in which rust is significantly left. is not.

  On the other hand, in recent years, in order to reduce the load on the environment, it is desired to minimize the use of organic solvents also in the field of anticorrosion paints.

  As materials that meet such demands, materials that are low in volatilization amount of organic solvent have been developed even with base conditioners for fixing rust.

  Patent Documents 3 and 4 disclose a water-based base modifier comprising at least one component selected from the group consisting of a water-dispersible polyisocyanate resin and an anticorrosive pigment, a corrosive ion fixing agent and a silane coupling agent. It is done. In addition, Patent Document 5 discloses at least one selected from the group consisting of bisphenol type epoxy resin, a specific reactive diluent having a glycidyl group, a curing agent, a rust preventive pigment, a corrosive ion fixing agent and a silane coupling agent. A substrate conditioner comprising the ingredients of

  The base conditioners described in Patent Documents 3 to 5 are water-based or solvent-free type, can penetrate rust sufficiently, and can fix rust, but a rust surface with a fragile rust surface or severe irregularities. On the other hand, when such a base conditioner is applied and then the paint is applied, there have been cases where cracking occurs in the process of forming a coating film with the paint.

  As described above, in the repair coating of a steel structure in which rust has occurred, not only the process of removing the rust is simplified, but also the demand for using an aqueous anticorrosion paint as a material is increasing. There is a need for development of applicable surface treatment methods and aqueous anticorrosion paints.

JP 2001-217645 A Unexamined-Japanese-Patent No. 6-334382 JP, 2017-141398, A Unexamined-Japanese-Patent No. 2017-66357 JP, 2016-194045, A

  The present invention is to propose an anticorrosion coating method using a simple surface treatment method for adjusting a rust surface to a state suitable for applying an aqueous coating composition.

  The inventors of the present invention have examined whether various types of rusted surfaces such as a fragile rusted surface and a strongly uneven rusted surface are in the state of a coated film with a water-based anticorrosion paint. Before applying the paint, it was first found that it is important to impregnate the air holes possessed by the rusted surface with the liquid.

  And the coating film formed by the aqueous | water-based anti-corrosion coating applied by the following process is coated by carrying out the foundation | substrate process which coats and impregnates the surface treatment liquid which contains a specific amount of organic solvents by a specific application amount on a rust surface. It discovered that corrosion resistance could be exhibited further.

That is, the present invention
1.
The coating amount of the surface treatment solution (A) containing the organic solvent (a1) and water on the rust surface and the amount of the organic solvent (a1) in the total treatment solution is in the range of 0.1 to 65% by mass The surface treatment process (1) which is painted in the range of 50-550 g / m < ² >, is impregnated, and carries out the surface treatment of a rust surface,
An undercoating step (2) of applying an aqueous anticorrosion paint (B) to the surface treated part obtained in the step (1),
Anti-corrosion coating method of rust surface.
2.
The anticorrosion coating method according to Item 1, wherein the aqueous anticorrosion paint (B) is applied to the substrate treatment liquid (A) after application and before complete drying.
3.
The corrosion preventing coating method according to item 1 or 2, wherein the surface treatment liquid (A) contains the aqueous anticorrosion paint (B) as a part of its components, and the nonvolatile content concentration is in the range of 2 to 50%. .
4.
The aqueous anticorrosion paint (B) is a two-component type, and the main component (I) contains an amino group-containing resin emulsion containing an epoxy resin as a production raw material, and the curing agent component (II) contains an epoxy group-containing resin emulsion The corrosion prevention coating method of any one of claim | item 1 thru | or 3.
5.
The anticorrosive coating method according to Item 4, wherein the amino group-containing resin emulsion uses, as a production raw material, a reactive group-containing softener capable of reacting with an amino group.
6.
The anticorrosion coating method according to Item 4 or 5, wherein the weight average molecular weight of the resin of the epoxy group-containing resin emulsion is lower than the weight average molecular weight of the resin of the amino group-containing resin emulsion.
7.
An anticorrosion pigment capable of eluting at least one ion selected from an aqueous anticorrosive paint (B) from magnesium ion, aluminum ion, calcium ion, zinc ion, silicate ion, phosphate ion, vanadate ion and molybdate ion 7. The anticorrosion coating method according to any one of items 1 to 6, including (b6-1),
8.
Item 8. A coated article to which the anticorrosion coating according to any one of Items 1 to 7 is applied.
About.

  According to the present invention, since the surface treatment of a rusted surface can be easily performed by a simple operation, there is an advantage that the burden on the operator is small. If the aqueous anticorrosion paint is applied after the rusted surface is treated by the method of the present invention, the amount of organic solvent released is small, the load on the environment is small, and the anticorrosion of the aqueous anticorrosion paint can be further enhanced.

  The coating film formed by the anticorrosion coating method described in the method of the present invention is free from coating film defects such as cracking and swelling, and can protect the substrate from external factors such as oxygen and water for a long time.

<Coated object>
The rust surface to which the method of the present invention is applied is not limited as long as it is a material having rust on the surface. The material includes metal materials such as steel, but is also applicable to non-ferrous metals such as zinc and aluminum.

  Specific examples of the substrate to which the method of the present invention is applied include structures using metals as materials, processed products processed into plates, rods, tubes, etc. For example, towers, bridges, tanks, etc. Civil engineering structures; Structures such as various plants such as oil and gas drilling plants; Architectural structures such as houses and buildings; Outdoor equipment such as guard fences and industrial machines. These to-be-coated-articles may be provided with the old coating film, as long as rust generate | occur | produced.

  Further, the rusted surface in the method of the present invention may be treated to partially remove the rust with a hand tool such as a scraper or a wire brush or an electric tool such as a disk sander, a wire cup, or an electric tongue. .

  The degree of occurrence of rust is not particularly limited, but, for example, the rust generation area ratio can be 3% or more, particularly 10% or more, more particularly 50% or more.

  The rusted area ratio is the percentage of the area of the rusted area to the area of the substrate, randomly taking five photographs after base adjustment, and calculating the area of the rusted area in each photograph, the average It can be determined by

  According to the method of the present invention, the effect can be exerted on a substrate where a large amount of rust has occurred. For this reason, it is possible to carry out the partial removal process of rust with a hand tool in a short time or to omit the partial removal process of rust itself. Such an advantage is particularly useful, for example, when the method of the present invention is applied to a substrate that is in an area where no power tools can be used, for example, when fire is prohibited.

<Base treatment process (1)>
In the present invention, an organic solvent (a1) and water are contained as a surface treatment liquid for direct coating on a rusted surface, and the amount of the organic solvent (a1) in the entire treatment liquid is 0.1 to 65% by mass. The surface treatment solution (A) is used.

<Base treatment liquid (A)>
Specific examples of the organic solvent (a1) which is an essential component of the surface treatment liquid (A) include alcohol compounds such as methanol, ethanol, isopropanol, n-butanol and isobutanol; dioxane, tetrahydrofuran, 3-methyl-3 Ether compounds such as methoxy butanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert -Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether Glycol ether compounds such as diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, and propylene glycol monoisopropyl ether;
Dipropylene glycol ether compounds such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether;
Ester compounds such as ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate and the like;
Methyl isopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl butyl ketone, ethyl propyl ketone, dipropyl ketone, ketone compounds such as methyl ethyl ketone, cyclohexanone, etc. are mentioned, and these are used singly or in combination of two or more be able to. As the organic solvent, it is preferable to use one having a boiling point of less than 200 ° C., particularly 80 to 190 ° C., from the viewpoint of long-term corrosion resistance, low temperature film forming property and the like. It is also preferred to use an organic solvent which dissolves at least 10 g, preferably 20 g, in 100 g of water at 20 ° C.

  The amount of the organic solvent (a1) in the surface treatment solution (A) in the method of the present invention is 0.1 to 65% by mass, and in particular 1 to 50% by mass is suitable.

  If the amount of the organic solvent (a1) is less than 0.1% by mass, the film forming property of the aqueous anticorrosion paint is insufficient, while if it exceeds 65% by mass, the dental caries drying property after coating the aqueous anticorrosion paint (B) And corrosion resistance is insufficient, which is not preferable.

The undercoating solution (A) contains water in addition to the organic solvent (a1). As water, either tap water or deionized water can be used, but usually deionized water is preferable.
The amount of water in the surface treatment liquid (A) is preferably 35% by mass or more, particularly 45 to 98% by mass.

  The surface treatment liquid (A) can also contain an aqueous anticorrosion paint (B) described below as long as it is within the scope of the present invention. In this case, the surface treatment liquid (A) is different from the aqueous anticorrosion paint (B) in that the non-volatile content concentration is lower than that of the aqueous anticorrosion paint (B). From the viewpoint of permeability to the rust layer, the concentration of non-volatile components in the case where the surface treatment liquid (A) contains the aqueous anticorrosion paint (B) is adjusted in the range of 2 to 50% by mass, in particular 5 to 40% by mass Is appropriate.

  In the present specification, the non-volatile content means a residue from which volatile components are removed, and the residue may be solid or liquid at normal temperature. For example, the sample is treated at 105 ° C. for 3 hours to remove remaining volatile components.

<Painting of surface treatment liquid (A)>
The surface treatment solution (A) is coated and impregnated on the rusted surface with a paint such as air spray, airless spray, brush coating, or roller. The coating amount of the undercoating liquid (A) is in the range of 50~550g / ^{m 2,} still good if in the range of from 100 to 400 g / ^{m 2.}

  If the coating amount is outside this range, physical properties such as corrosion resistance, moisture resistance and adhesion of the coating film obtained by coating the aqueous anticorrosion paint (B), which is the next step, become insufficient, which is not preferable.

In the present specification, the coating amount (g / m ² ) is a value calculated by dividing the mass of the surface treatment liquid (A) used for coating on the substrate by the coating area. The mass of the base treatment liquid (A) used to apply on the substrate can be determined by measuring the weight of the coating tool before and after coating and the weight loss of the base treatment liquid (A) used.

  It is preferable to perform coating of the aqueous anticorrosion paint (B) before complete drying after the surface treatment liquid (A) coating. It is because the effect which performed the base-treatment process (1) can not be exhibited if it is made to completely dry after painting with a base-treatment liquid (A).

  In the present specification, complete drying means a state in which no volatile component remains, and the state can be obtained by adjusting the coating amount of the surface treatment liquid (A) in the above range. In particular, in the present invention, it is important that the organic solvent (a1) and water remain on the rusted surface when the aqueous anticorrosion paint (B) is applied. This is because the surface treatment solution (A) is present in the pits of the rust, the aqueous anticorrosion paint (B) coated on the rust surface can be drawn into the pits of the rust, and the aqueous anticorrosion paint (B) is rusted It is thought that it is useful for instilling deep into the

  In the present invention, when the coating amount of the surface treatment solution (A) is within the range of the present invention, the aqueous anticorrosion paint (B) can be applied immediately, but depending on the case or when necessary it is left at normal temperature. Or, it is also possible to force-dry a part of the surface treatment unit with the treatment liquid (A). When leaving at normal temperature, as a specific leaving time, although it changes with coating environment and a season, as an example, leaving for 1 minute-1 hour is mentioned, for example.

<Undercoating process (2)>
The undercoating step (2) in the anticorrosion coating method of the present invention is a step of applying the aqueous anticorrosion paint (B) to the surface treated portion treated in the above-mentioned surface treatment step (1).

<Water-based anticorrosive paint (B)>
As the aqueous anticorrosion paint (B) used in the undercoating step, any form of paint such as water dispersion type or water solubility can be used as long as it is a paint containing water as a main medium. In particular, a room temperature drying type water-based paint containing a mixture of one or more of resins such as oil-modified resin, alkyd resin, epoxy resin, vinyl resin and acrylic resin as a resin component is preferable. Among these, a two-component epoxy resin-based paint is suitable from the point of corrosion resistance.

  The epoxy resin-based paint refers to a paint containing 5% or more of an epoxy group-containing resin as a part of the binder component.

  In the method of the present invention, the aqueous anticorrosion paint (B) is a two-component type, and the main component contains an amino group-containing resin emulsion containing an epoxy resin and a polyamine compound as manufacturing raw materials, and a curing agent component contains the epoxy group-containing resin emulsion. It is preferable that it is a containing paint.

<Amino group-containing resin emulsion>
The amino group-containing resin emulsion used in the aqueous anticorrosion paint (B) of the present invention is suitably a resin having an epoxy resin (b1) and a polyamine compound (b2) as a raw material for production, and the total amine value of the resin Preferably, it is in the range of 20 to 120 mg KOH / g.

<< Epoxy resin (b1) >>
The epoxy resin (b1) as a raw material for producing an amino group-containing resin emulsion is a resin having at least one, preferably two or more epoxy groups in the molecule, and is at least 160, preferably in the range of 180-2500. Those having an epoxy equivalent of are suitable.

  Specific examples of the epoxy resin (b1) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin; epoxy ester obtained by modifying the bisphenol-type epoxy resin with a dibasic acid or the like. Resins; novolac epoxy resins such as cresol novolac epoxy resins and phenol novolac epoxy resins; alicyclic epoxy resins; polyglycol epoxy resins; hydrogenated bisphenol A epoxy resins; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Aliphatic epoxy such as glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether Examples thereof include resins and epoxy group-containing acrylic resins having an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate as a component. As an epoxy resin, an unmodified epoxy resin is preferable. These can be used alone or in combination of two or more.

  As a commercial item of the above-mentioned epoxy resin (b1), for example, “jER 827”, “jER 828”, “jER 828 EL”, “jER 828 XA”, “jER 834” (above, manufactured by Mitsubishi Chemical Corporation), “EPICLON 840”, “EPICLON 840-S "EPICLON 850", "EPICLON 850-S", "EPICLON 850-CRP", "EPICLON 850-LC" (above, made by DIC Corporation), "Epotote YD-127", "Epotote YD-128" (above, Toto Kasei Co., Ltd.) Bisphenol A type epoxy resins such as “Rica Resin BPO-20E” and “Rica Resin BEO-60E” (all manufactured by Shin Nippon Chemical Co., Ltd.); “jER806”, “jER 807” (All manufactured by Mitsubishi Chemical Corporation), EPICLON 830 "," EPIC Bisphenol F type epoxy resin such as ON 830-S "," EPICLON 835 "(above, made by DIC)," Epotote YDF-170 "(made by Tohto Kasei Co., Ltd.); Bisphenol A such as" jER 4250 "(made by Mitsubishi Chemical Corporation) Bisphenol F type phenoxy resin, novolak type epoxy resin such as "jER152" (made by Mitsubishi Chemical Corporation); "jERYX 8000", "jERYX8034" (above, made by Mitsubishi Chemical Corporation), "Epototo ST-3000" (made by Toto Kasei Co., Ltd.) Hydrogenated bisphenol A type such as “Rica resin HBE-100” (manufactured by Shin Nippon Rika Co., Ltd.) “Denacol EX-252” (all manufactured by Nagase ChemteX Co., Ltd.), “SR-HBA” (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) Epoxy resin; “YED205”, “YED216M”, “YED216D” ( Above, made by Mitsubishi Chemical Corporation, “Epotote YH-300”, “Epotote YH-301”, “Epotote YH-315”, “Epotote YH-324”, “Epotote YH-325” (all manufactured by Toto Kasei Co., Ltd.) , "Dena call EX-211", "Dena call EX-212", "Dena call EX-212 L", "Dena call EX-214 L", "Dena call EX-216 L", "Dena call EX-313", "Dena call EX-314", "Dena call EX-321", "Dena call EX-321 L", "Dena call EX-411", "Dena call EX-421", "Dena call EX-512", "Dena call EX-521", "Dena call EX-611", " Dena call EX-612, Dena call EX-614, Dena call EX-614 B "," Dena call EX-622 "," Dena call EX-810 "," Dena call EX-811 "," Dena call EX-850 "," Dena call EX-850 L "," Dena call EX-851 "," Dena call EX-821 "," Dena call EX-830 "," Dena call EX-832 "," Dena call EX-841 "," Dena call EX-861 "," Dena call EX-911 "," Dena call EX-941 "," Dena call EX-920 ", "Denacol EX-931" (above, Nagase ChemteX Co., Ltd.), "SR-NPG", "SR-16H", "SR-16HL", "SR-TMP", "SR-PG", "SR-TPG" “SR-4PG”, “SR-2EG”, “SR-8EG”, “SR-8EGS”, “SR-GLG”, “SR- GE "," SR-DGE "," SR-4GL "," SR-4GLS "," SR-SEP "(or, BanHajime manufactured Yakuhin Kogyo Co., Ltd.) aliphatic epoxy resins such as are exemplified.

  The above epoxy resin (b1) reacts the above exemplified epoxy resin with a bifunctional polyester polyol, a bifunctional polyether polyol, a bisphenol, a dibasic carboxylic acid, etc. so that the epoxy group becomes excessive. Also included are epoxy resins obtained by

<< Polyamine compound (b2) >>
The polyamine compound (b2) constituting the amino group-containing resin emulsion is a polyamine compound (b2-1) having a primary amino group at both molecular ends and at least one secondary amino group desirable.

  Examples of such a polyamine compound (b2-1) include dimethylene triamine, diethylene triamine, dipropylene triamine, dibutylene triamine, dialkylene triamine such as bis (hexamethylene) triamine; triethylene tetramine, tripropylene tetramine and the like Examples include trialkylenetetramine; tetraalkylenepentamine such as tetraethylenepentamine and tetrapropylpentamine; pentaalkylenehexamine; hexaalkylene heptamine and the like. These can be used singly or in combination of two or more.

  In the present invention, in particular, the polyamine compound (b2-1) is preferably a dialkylene triamine from the viewpoint of production and storage stability of the main ingredient (I) and corrosion resistance on a rust surface, and the carbon number is 2 to 8 Particularly suitable are dialkylene triamines, preferably having 3 to 6 alkylene groups.

  Moreover, as a polyamine applicable other than the said polyamine compound (b2-1), a monomethylamine, a dimethylamine, a monoethylamine, a diethylamine, a dipropylamine, a dibutylamine, a dihexylamine, a dioctylamine, monoisopropylamine, a diisopropylamine, for example is mentioned. Mono-alkylamine or di-alkylamine such as monobutylamine, monooctylamine, methylbutylamine and dibutylamine; monoethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, mono (2-hydroxypropyl) Amine, di (2-hydroxypropyl) amine, N-butylethanolamine, dipropanolamine, monomethylaminoethanol, N- (2-hydroxypropyl) Alkanolamines such as tilylenediamine, 3-methylamine-1,2-propanediol, 3-tert-butylamino-1,2-propanediol, N-methylglucamine, N-octylglucamine, etc .; polymethylene diamine, poly Ether diamines, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, dimethylaminopropyl amine, diethylaminopropyl amine, alkylenepolyamines such as bis (4-aminobutyl) amine; mensene diamine, isophorone diamine, bis (4-Amino-3-methylcyclohexyl) methane, metaxylylenediamine, metaphenylenediamine, naphthalenediamine, dimethylaminomethylbenzene, and other aromatic or alicyclic poly Min; piperazine, 1-methyl piperazine, 3-pyrrolidinol, 3-piperidinol, polyamine having a heterocyclic ring such as 3-pyrrolidinol; epoxy addition polyamine obtained by adding an epoxy group-containing compound to 1 mol of the above polyamine One or more in one molecule of polyamide resin formed by the condensation of the above-mentioned polyamine with an aromatic acid anhydride, a cyclic aliphatic acid anhydride, an aliphatic acid anhydride, a halogenated acid anhydride and / or a dimer acid And polyamide polyamines containing secondary or secondary amines; ketimined amines obtained by reacting one or more primary or secondary amines in the above polyamines with ketone compounds; and the like. These can be used singly or in combination of two or more.

  The proportion of the epoxy resin (b1) and the polyamine compound (b2) used is 0.2 to 3.0 mol, preferably 0.5 to 2. mol of the polyamine compound (b2) per 1 mol of the epoxy resin (b1). It is suitable that the ratio is 5 moles.

<< Ketone compound (b3) >>
Further, the amino group-containing resin emulsion is preferably a resin which uses the ketone compound (b3) as a production raw material in addition to the epoxy resin (b1) and the polyamine compound (b2).

  Examples of the ketone compound (b3) include methyl isopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl butyl ketone, ethyl propyl ketone, dipropyl ketone, methyl ethyl ketone and the like. These can be used alone or in combination of two or more. Among them, methyl isobutyl ketone is preferred.

  When the ketone compound (b3) is used, the use ratio in that case is 0.2 to 3.0 mol, preferably 0.5 to 2. mol per 1 mol of primary amino group in the polyamine compound (b2). It is suitable that the ratio is 5 moles.

<< Reactive Softener (b4) >>
In addition, the amino group-containing resin emulsion is a reactive group-containing softener (b4) modified resin emulsion using as a raw material a reactive group-containing softener (b4) having a reactive group capable of reacting with an amino group. Is suitable. The curing agent component (II) described later contains the softening agent (b5) and the functional group contained in the amino group-containing resin emulsion partially reacts with the reactive group-containing softening agent (b4), whereby the composition of the present invention It is effective in the improvement of the corrosion resistance of the coating film formed by the object.

  The reactive group-containing softener (b4) may be a compound having a functional group capable of reacting with an alkyl group having 4 or more carbon atoms and an amino group.

The reactive group-containing softener (b4) can be a compound having a functional group such as a carboxyl group and / or a glycidyl group, and specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Glycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl Ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, butyl glycidyl ether, 2-ethyl hexene Glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, cresyl glycidyl ether, alkyl glycidyl ether compounds such as tert- butylphenyl glycidyl ether;
Glycidyl butyric acid butyrate, stearic acid glycidyl ester, neodecanoate glycidyl ester, epoxidized soybean oil, epoxy butyl stearate, di 2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, Alkyl glycidyl ester compounds such as epoxidized decyl oleate;
Coconut oil fatty acid, cotton seed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, soy sauce fatty acid, rapeseed fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid And long-chain alkyl fatty acids such as;

  In the case of using a reactive group-containing softener (b4) as a raw material for production of an amino group-containing resin emulsion, the usage ratio in that case is 1 mol of primary amino group contained in the polyamine compound (b2) The functional group capable of reacting with the amino group contained in the compound (b4) is suitably in the range of 0.1 to 0.8 mol, preferably 0.2 to 0.6 mol.

  When the reaction ratio of the reactive group-containing softener (b4) to the polyamine compound (b2) falls within the above range, the coating film formed from the aqueous coating composition of the present invention is excellent in film forming property and excellent corrosion resistance Can be demonstrated.

  In the present invention, the amino group-containing resin emulsion may contain the above components (b1) and (b2) and, if necessary, (b3) and / or (b4) as a raw material for production, and surfactants and the like Other components can be used as manufacturing materials as required. The production method is not particularly limited, and the primary amino group of the polyamine compound (b2) is reacted with the ketone compound (b3) to be ketimidated, and then the secondary amino group and the epoxy group of the epoxy resin (b1) are reacted. Then, when diluting with water, the production method etc. which return ketimine to a primary amino group by hydrolysis etc. are mentioned.

  According to the above production method, the amino group-containing resin emulsion can have a primary amino group which is a water-dispersed group at the resin end in the presence of water, and forms an anticorrosion coating excellent in anticorrosion on a rusted surface To help.

  The surfactant used as required is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, Polyoxyethylene sorbitan alkyl esters, glycerin esters and derivatives thereof, alkyl benzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acids or Ester salt, alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl Anionic surfactants such as phosphoric acid esters or salts thereof, alkenyl phosphoric acid esters or salts thereof; Cationic surfactants such as quaternary ammonium salts; Carboxyl-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, etc. Amphoteric surfactant and the like.

  When mix | blending the said surfactant, you may carry out not only in the resin manufacture stage but at any stage of a coating manufacturing process. The compounding amount is 1 to 15 parts by mass, particularly based on 100 parts by mass in total of nonvolatile components of the amino group-containing resin emulsion and the epoxy group-containing resin emulsion, from the viewpoint of storage stability in the paint state and corrosion resistance of the formed coating film The range of 3-8 mass parts is suitable.

  Moreover, when using a compound (b4) as a manufacturing raw material, although it is possible to use in any step in manufacture of an amino group containing resin emulsion, the primary amino group of a polyamine compound (b2) is a ketone compound (b3) And react with the epoxy group of the epoxy resin (b1), and then, upon dilution with water, the ketimine is converted back to a primary amine by hydrolysis, and then the compound (b4) is reacted. The preferred method is

  The above-mentioned amino group-containing resin emulsion is well dispersed in an aqueous medium due to the presence of the amino group which may be neutralized. In the case of the aqueous dispersion, it is generally suitable that the average particle diameter is in the range of 50 to 500 nm, particularly 100 to 300 nm from the viewpoint of film forming ability and curability at normal temperature drying.

  As a neutralizing agent used for neutralization, for example, formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, glutaric acid, adipic acid, maleic acid, maleic acid, lactic acid, propionic acid, hydroxyethane diphosphonic acid And acid compounds such as organic acids such as methanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, zircohydrofluoric acid, silicohydrofluoric acid and nitric acid;

  The amino group-containing resin emulsion suitably has a total amine number in the range of 20 to 120 mg KOH / g, preferably 40 to 100 mg KOH / g.

  The amino group-containing resin emulsion is suitable in terms of coating physical properties such as normal temperature drying property, corrosion resistance and moisture resistance that the weight average molecular weight is in the range of 1000 to 20000, preferably 2000 to 8000. .

  In the present specification, the average particle size is a value of volume average particle size measured by Coulter counter method at a measurement temperature of 20 ° C. The measurement by the Coulter counter method can be performed, for example, using “COULTER N4” (trade name, manufactured by Beckman Coulter, Inc.).

  Moreover, an amine titer is measured according to JIS K 7237-1995. All are the amine value (mg KOH / g) per resin non volatile matter.

  The weight average molecular weight is calculated by converting the retention time (retention capacity) measured using gel permeation chromatography (GPC) into the molecular weight of polystyrene by the retention time (retention capacity) of standard polystyrene of known molecular weight measured under the same conditions. It is a value obtained by The columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all are manufactured by Tosoh Corp., trade names) Tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector; RI conditions were used.

<Epoxy group-containing resin emulsion>
In the present invention, as a raw material for producing the epoxy group-containing resin emulsion, the epoxy group-containing compounds listed in the description of the epoxy resin (b1) can be exemplified.

  Among them, the epoxy group-containing resin emulsion has a large number of epoxy groups capable of reacting with the amino group contained in the above-mentioned amino group-containing resin emulsion and is excellent in curability. It is preferable to contain a resin.

  The epoxy equivalent of the epoxy resin emulsion is suitably lower than that of the epoxy resin (b1) in the amino group-containing resin emulsion from the viewpoint of the compatibility between the main ingredient (I) and the curing agent component (II). In particular, it is suitable to be in the range of at least 50, preferably 100-500.

  In the present invention, the weight average molecular weight of the resin of the epoxy group-containing resin emulsion is suitably lower than that of the amino group-containing resin emulsion. Thereby, it is considered that the compatibility between the main component (I) of the aqueous anticorrosion paint (B) and the curing agent component (II) is further improved. The weight average molecular weight of the resin of the epoxy group-containing resin emulsion is not particularly limited, and specifically, it is suitably in the range of 300 to 10,000, preferably 500 to 5,000.

  The above epoxy group-containing resin emulsion is dispersed by a dispersion stabilizer or surfactant having an anionic, nonionic or cationic hydrophilic group, or the epoxy group-containing resin itself has these hydrophilic groups. The presence of these components allows the epoxy group-containing resin emulsion to be well dispersed in an aqueous medium.

  An acidic group is mentioned as an example of the said anionic hydrophilic group. Examples of the acidic group include carboxyl group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group and the like.

  Examples of the nonionic hydrophilic group include polyoxyalkylene groups and polyglycerin groups.

  Examples of the cationic hydrophilic group include primary to tertiary amino groups, an ammonium group, a pyridinium group, a sulfonium group, and a phosphonium group.

  The average particle diameter of the epoxy group-containing resin emulsion can be in the range of 50 to 1500 nm, preferably 200 to 1000 nm, when dispersed in an aqueous medium. When the average particle diameter is in this range, there is an effect that the film forming property of the composition after the mixture of the main agent component (I) and the curing agent component (II) is excellent. In particular, in the present invention, it is suitable that the average particle size of the epoxy group-containing resin emulsion is larger than the average particle size of the aqueous dispersion of the amino group-containing resin emulsion from the viewpoint of the film forming property of the aqueous anticorrosive paint (B).

  A commercial item can also be used for the said epoxy group containing resin emulsion. As a specific example, Waterzole series (made by DIC, trade name), Modepics series (made by Arakawa Chemical, trade name), Adeka Resin (made by Adeka, trade name), "Yuka resin KE-278", "Yuka resin" KE-002 "Yuka resin KE-307-2" (Yoshimura oil chemical company make, brand name) etc. can be mentioned.

<< Softener (b5) >>
Moreover, in the said water-based anticorrosion paint (B), it is suitable to contain a softener (b5) from the point of the film formability in a low temperature environment etc. As the softener (b5), a compound having good mixing stability with the epoxy group-containing resin emulsion is suitably used.

  In the present specification, in the state where the mixing stability of the epoxy group-containing resin emulsion and the softening agent (b5) is good, both are mixed in equal amounts, stirred until it becomes uniform visually, and left at 20 ° C. for 24 hours Sometimes it means that they are not separated.

  As such a softener (b5), an organic compound which is liquid at normal temperature and whose weight average molecular weight is equal to or less than that of the resin of the epoxy group-containing resin emulsion is suitable. Specifically, glycol ether compounds, alkyl ester compounds, epoxy compounds and the like can be mentioned.

  Examples of glycol ether compounds include diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monopropyl ether, Propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexyl glycol and the like can be mentioned.

  As an alkyl ester compound, dibutyl adipate, DBE (dibasic acid ester), dibutyl phthalate, di 2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, diheptyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, ethyl phthalyl Ethyl glycolate, di-2-ethylhexyl adipate, dibutyl diglycol adipate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobu Thiolate, 2,2,4-trimethyl-1,3-pentanediol 2-ethylhexanoate isobutyrate, 2,2,4-trimethyl-1,3-pentanediol di 2-ethylhexanoate, etc. List It is possible.

  As an epoxy compound, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether , Cresyl glycidyl ae Alkyl glycidyl ether compounds such as tert-butylphenyl glycidyl ether; butyric acid glycidyl ester, stearic acid glycidyl ester, neodecanoic acid glycidyl ester, epoxidized soybean oil, epoxy butyl stearate, epoxy hexahydrophthalic acid di 2-ethylhexyl, epoxy Examples thereof include alkyl glycidyl ester compounds such as diisodecyl hexahydrophthalic acid, epoxy triglyceride, epoxidized octyl oleate and epoxidized decyl oleate. The above compounds can be used alone or in combination of two or more.

Among the above, it is suitable to use an epoxy compound from the point of corrosion resistance.
The proportion of the softener (b5) in the total amount of the curing agent component (II) in the present invention is suitably in the range of 1 to 30% by mass, in particular 5 to 20% by mass.

<< Antirust pigment component (b6) >>
In the aqueous anticorrosion paint (B), it is preferable that the main ingredient (I) and / or the curing agent component (II), preferably the main ingredient (I), further contain a rust preventive pigment component (b6).

  In the present invention, the antirust pigment component (b6) is at least one selected from magnesium ion, aluminum ion, calcium ion, zinc ion, silicate ion, phosphate ion, vanadate ion and molybdate ion in a corrosive environment. It is preferable that the anticorrosion pigment (b6-1) capable of eluting ions of When the rustproof pigment component (b6) contains the above-mentioned specified rustproof pigment (b6-1), the above-mentioned ions are eluted when the coating film coated on the rust surface or on the metal substrate is lost, The corrosion resistance can be more effectively exhibited by acting on the defective portion.

  In the present invention, the presence or absence of ion elution of the rust preventive pigment (b6-1) is determined, for example, by eluting the rust preventive pigment (b6-1) in a sodium chloride aqueous solution and measuring the elution amount by ICP emission spectral analysis. Is possible. More specifically, 10% by mass of a rust preventive pigment (b6-1) was added to a 5% by mass aqueous solution of sodium chloride, stirred at 25 ° C. for 6 hours, and allowed to stand for 24 hours to remove precipitates There is a method of detecting the supernatant by the presence or absence of the dissolved element amount measured by ICP emission spectral analysis.

  In the present invention, depending on the form in which the main ingredient (I) contains the rust-preventive pigment component (b6) together with the amino group-containing resin emulsion, the main ingredient (I) can contain the rust-preventive pigment component (b6) in a sufficient amount. Production and storage stability are good, and the coating film formed from the aqueous anticorrosion paint (B) can exhibit stable corrosion resistance.

As a specific example of the rust preventive pigment (b6-1) which may be contained in the rust preventive pigment component (b6), a single compound, a composite compound, and a composition in which a plurality of these compounds are used in combination There is no restriction on its form, etc. Specifically, zinc phosphate, magnesium phosphate, magnesium ammonium phosphate coprecipitate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium phosphate calcium precipitate Magnesium phosphate / cobalt coprecipitate, magnesium phosphate / nickel coprecipitate, calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate difluoride, aluminum phosphate, hydrogen phosphate Phosphoric metal compounds such as aluminum;
Phosphorous acid metal compounds such as magnesium phosphite, calcium phosphite, magnesium phosphite calcium co-precipitate, basic zinc phosphite, barium phosphite, manganese phosphite, calcium phosphite and the like;
Calcium silicate, zinc silicate, aluminum silicate, aluminum orthosilicate, hydrated aluminum silicate, aluminosilicate, borosilicate, beryllosilicate, calcium aluminum silicate, sodium aluminum silicate, beryllium aluminum silicate, silica Silicates such as sodium silicate, calcium orthosilicate, calcium metasilicate, calcium sodium silicate, zirconium silicate, magnesium orthosilicate, magnesium metasilicate, magnesium calcium silicate, manganese silicate, barium silicate etc; magnesium ion exchange Metal ion exchange silica compounds such as silica, calcium ion exchange silica, etc.
Condensed phosphoric acid based metal compounds such as aluminum tripolyphosphate, magnesium tripolyphosphate, aluminum tripolyphosphate, zinc dihydrogen tripolyphosphate and the like;
Vanadium metal compounds such as vanadium pentoxide, calcium vanadate, magnesium vanadate and ammonium metavanadate, calcined products of manganese oxide and vanadium oxide, calcined products of calcium phosphate and vanadium oxide, etc.
Molybdic acid metal compounds such as aluminum molybdate, calcium molybdate, aluminum phosphomolybdate;
Zinc compounds such as zinc and zinc oxide;
Silica-based compounds such as silica and colloidal silica;
Complex metal oxides such as complex oxides of iron oxide and magnesium oxide, complex oxides of iron oxide and calcium oxide, complex oxides of iron oxide and zinc oxide;
Etc. can be mentioned. As described above, these may be used alone or in combination of two or more, or may be a composite of two or more. In addition, modified compounds or treated products of these exemplified compounds with silica compounds such as silica, calcium silicate and the like and magnesium oxide and the like are also included in the rust preventive pigment (b6-1).

  In particular, in the present invention, the rust preventive pigment (b6-1) is a component capable of eluting at least one metal ion selected from silicate ions and / or phosphate ions and magnesium ions, aluminum ions, calcium ions and zinc ions. It is excellent in point rust suppression property and the corrosion resistance with respect to a rust surface and a metal surface exposed part, and it is suitable. That is, in the present invention, the rust preventive pigment (b6-1) is a component capable of eluting [1] silicate ion, and at least one metal ion selected from magnesium ion, aluminum ion, calcium ion and zinc ion Or [2] a component capable of eluting phosphate ion, and a component capable of eluting at least one metal ion selected from magnesium ion, aluminum ion, calcium ion and zinc ion, or 3) A component capable of eluting silicate ions and phosphate ions, and any component capable of eluting at least one metal ion selected from magnesium ions, aluminum ions, calcium ions and zinc ions Is suitable.

  In particular, an embodiment in which the rust preventive pigment (b6-1) is a component capable of eluting silicate ions and phosphate ions and at least one metal ion selected from magnesium ions, aluminum ions, calcium ions and zinc ions Is suitable. That is, it is a component capable of eluting silicate ions and phosphate ions, and a component capable of eluting at least one metal ion selected from magnesium ions, aluminum ions, calcium ions and zinc ions, in particular Is suitable.

  The form of such an antirust pigment (b6-1) is not limited as long as it can elute both a silicate ion and / or a phosphate ion and a metal ion as described above, and the form thereof is not limited, and a single compound or a composite compound It may be present, or it may be a composition in which a plurality of the compounds described above are combined. For example, the combination of magnesium oxide treated product of aluminum tripolyphosphate dihydrogen phosphate and magnesium ion-exchanged silica is a silicate ion and a phosphate ion, and at least one metal selected from magnesium ion, aluminum ion, calcium ion and zinc ion It is an example of the antirust pigment (b6-1) which can elute ion.

  Among the rust preventive pigments (b6-1), the rust preventive pigment capable of eluting silicate ions may contain a siliceous compound capable of eluting silicate ions in a corrosive environment. For example, silica, colloidal silica, a compound listed in the explanation of the rust preventive pigment (b6-1) described above modified with a silicate compound, magnesium ion exchanged silica, calcium ion exchanged silica, vanadium ion exchanged silica, metal ion exchanged silica There can be mentioned, for example, based compounds. These can be used alone or in combination of two or more.

  The rust preventive pigment capable of eluting phosphate ion may contain a phosphate compound capable of eluting phosphate ion in a corrosive environment. For example, magnesium phosphate, magnesium magnesium ammonium co-precipitate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium calcium phosphate co-precipitate, magnesium phosphate cobalt co-precipitate, magnesium phosphate nickel Co-precipitates, magnesium phosphite, magnesium phosphite / calcium co-precipitate, magnesium tripolyphosphate, magnesium oxide-treated tripolyphosphate dihydrogen aluminum, magnesium trioxide-dihydrogen zinc dihydrogen phosphate, magnesium vanadate, etc. It can be mentioned. These can be used alone or in combination of two or more.

  The anticorrosive pigment capable of eluting magnesium ions may contain a magnesium compound capable of eluting magnesium ions in a corrosive environment. Specifically, for example, compounds obtained by treating the compounds listed in the explanation of the above-mentioned rust preventive pigment (b6-1) with magnesium oxide, magnesium phosphate, magnesium phosphate ammonium coprecipitate, magnesium monohydrogen phosphate, phosphorus Magnesium dihydrogen phosphate, magnesium phosphate / calcium co-precipitate, magnesium phosphate / cobalt co-precipitate, magnesium phosphate / nickel co-precipitate, magnesium phosphite, magnesium phosphite / calcium co-precipitate, magnesium ion exchange Silica, magnesium tripolyphosphate, magnesium vanadate, magnesium metasilicate, magnesium calcium silicate, iron oxide and magnesium oxide composite oxide, magnesium vanadate and the like can be mentioned. These can be used alone or in combination of two or more.

  The anticorrosion pigment capable of eluting aluminum ions may contain an aluminum compound capable of eluting aluminum ions in a corrosive environment. For example, aluminum phosphate, aluminum hydrogen phosphate, aluminum tripolyphosphate, aluminum tripolyphosphate, aluminum molybdate, aluminum silicate, aluminum orthosilicate, hydrated aluminum silicate, aluminosilicate, aluminum calcium silicate, silicate Aluminum sodium, aluminum beryllium aluminum silicate, aluminum phosphomolybdate, aluminum vanadate and the like can be mentioned. These can be used alone or in combination of two or more.

  The anticorrosive pigment capable of eluting calcium ion may contain a calcium compound capable of eluting calcium ion in a corrosive environment. For example, magnesium phosphate / calcium co-precipitate, calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate difluoride, calcium phosphite, calcium phosphite / magnesium calcium co-precipitate, hypophosphite Calcium phosphate, calcium ion exchange silica, calcium vanadate, calcined product of calcium phosphate and vanadium oxide, calcium molybdate, iron oxide and calcium oxide complex oxide, calcium silicate, calcium aluminum silicate, calcium orthosilicate, calcium metasilicate, Calcium sodium silicate, magnesium calcium silicate, calcium vanadate and the like can be mentioned. These can be used alone or in combination of two or more.

  The anticorrosion pigment capable of eluting zinc ion may contain a zinc compound capable of eluting zinc ion in a corrosive environment. For example, complex metal oxides such as zinc, zinc oxide, zinc phosphate, basic zinc phosphite, zinc tripolyphosphate, zinc silicate, zinc vanadate, complex oxides of iron oxide and zinc oxide, etc. It can be mentioned. These can be used alone or in combination of two or more.

  The anticorrosion pigment component (b6) used in the present invention can contain other anticorrosion pigments other than the anticorrosion pigment (b6-1) as required. Specific examples of such other anti-corrosive pigments include cobalt compounds such as vanadium pentoxide and cobalt hydroxide; boric acid compounds such as barium metaborate; iron phosphide, manganese phosphide, nickel phosphide, cobalt phosphide And phosphide such as copper phosphide and the like.

  When other rust preventive pigments are used, the amount used in that case can be 30% by mass or less in the rust preventive pigment component (b6).

  The anticorrosive pigment component (b6) may be used alone or in combination of two or more commercial products. As such commercially available products, for example, "EXPERT NP-1000", "EXPERT NP-1020C", "EXPERT NP-1100", "EXPERT NP-1102" (all manufactured by Toho Pigment Industry Co., Ltd., trade names), "LF BOSEY" "CP-Z", "LF Bowse MZP-500", "LF Bowsei CRFC-1", "LF Bowsei M-PSN", "LF Bowsay MC-400WR", "LF Bowsay PM-300", "LF Bowsay PM-" 308 "(manufactured by Kikuchi Color, Inc., trade name)," K-WHITE 140 "," K-WHITE Ca 650 "," K-WHITE 450 H "," K-WHITE G-105 "," K-WHITE # 105 "," K-WHITE # 82 "(above, made by Tayca, product name)," SHIELDEX C303 "," S HIELDEX AC-3 "," SHIELDEX C-5 "(all are manufactured by W. R. Grace & Co.," Silo Mask 52 "," Silo Mask 52 M "," Silo Mask 22 MR-H "," Silo Mask Mg " (Manufactured by Fuji Silysia Chemical Co., Ltd.), "Novinox ACE-110" (manufactured by SNCZ, France), and the like.

  The compounding amount of the above-mentioned antirust pigment component (b6) is 1 to 100 parts by mass, preferably 5 to 90 parts by mass, more preferably 10 to 80 parts by mass based on 100 parts by mass of the amino group-containing resin emulsion nonvolatiles It is suitable to be in the range of

<< Fiber-like inorganic compound (b7) >>
In the aqueous anticorrosion paint (B), it is preferable that the main ingredient (I) and / or the curing agent component (II), preferably the main ingredient (I), further contain a fibrous inorganic compound (b7).

  The reason is not clear, but the fibrous inorganic compound (b7) has the effect of improving the adhesion to the rusted surface and the corrosion resistance.

  The fibrous inorganic compound (b7) is not particularly limited in its material, manufacturing method, place of production, etc. Specific examples thereof include glass fiber, silicon carbide, silicon nitride, wollastonite, sepiolite, chrysotile, amosite, tremolite , Zeolite, calcium metasilicate, zonolite, potassium titanate, rock wool, aluminum silicate, carbon fiber, aramid fiber, aluminum borate, calcium carbonate, needle basic magnesium sulfate, glass flake, zinc oxide, aragonite Type light calcium carbonate, spindle type light calcium carbonate, satin white and the like. These can be used alone or in combination of two or more.

  In the present invention, as the above fibrous inorganic compound (b7), one having an aspect ratio of 3.5 or more, preferably in the range of 4 to 25 is preferably used.

  The aspect ratio is the value of the major axis diameter / minor axis diameter of the inorganic acicular pigment, and the minor axis diameter and the major axis diameter referred to herein are each of 100 primary particles present in a certain area by electron microscopic observation. The minor axis diameter and the major axis diameter of were measured, and the respective number average values were determined.

  The average fiber length of the fibrous inorganic compound (b7) is preferably 5 to 300 μm, and more preferably 10 to 200 μm. In the present specification, the average fiber length is the average value of the major axis diameter obtained in the measurement of the aspect ratio.

  In the present invention, the blending amount of the fibrous inorganic compound (b7) is in the range of 0.1 to 30 parts by mass, preferably 5 to 25 parts by mass, based on 100 parts by mass of the total non-volatiles of the resin contained in the coating It is suitable to be inside.

<< Polycarbodiimide Compound (b8) >>
In addition, the main ingredient component (I) and / or the curing agent component (II), preferably the curing agent component (II) preferably further contains a polycarbodiimide compound (b8).

  The inclusion of the polycarbodiimide compound (b8) in the aqueous anticorrosion paint (B) is effective in improving the moisture resistance of the formed coating.

  The polycarbodiimide compound (b8) is a polymer having -N = C = N- group in the molecule, and can be produced, for example, by a decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst. Carbodiimidization catalysts include tin, magnesium oxide, potassium ions, 18-crown-6, 3-methyl-1-phenyl-2-phospholene oxide, and the like, and combinations thereof. These can be used alone or in combination of two or more.

  Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3-Bis (isocyanatomethyl) cyclohexane, tetramethyl xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 1,12-diisocyanate Dodecane, 2,4-bis- (8-isocyanatooctyl) -1,3-dioctylcyclobutane, n-penta Carbodiimidization by subjecting one or two or more of polyfunctional isocyanates such as benzene-1,4-diisocyanate to a decarbon dioxide condensation reaction to form a terminal residual isocyanate group as a hydrophilic group in order to impart water reducibility Sealed.

  Examples of the hydrophilic group to be sealed include residues of alkyl sulfonates, quaternary salts of residues of dialkylamino alcohols, and residues of polyoxyalkylenes whose alkoxy group ends are blocked.

  As a polycarbodiimide compound, for example, "Carbodilite V-02", "Carbodilite V-04", "Carbodilite V-02-L2", "Carbodilite E-02", "Carbodilite E-03A", "Elastostab H01" ( As mentioned above, commercial products, such as a product name and Nisshinbo Chemical Co., Ltd. make, can be used.

  The compounding amount of the polycarbodiimide compound (b8) is in the range of 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the resin non volatile matter contained in the aqueous coating composition Some are suitable from the point of water absorption and corrosion resistance of the coating.

  In the above aqueous anticorrosion paint (B), a color pigment, an extender, a pigment dispersant, an organic solvent, a surface control agent, an antifoamer, a thickener, a curing catalyst, a surfactant, an antisettling agent, a plasticizer, a reaction Conventional paint additives such as basic diluents, antifreeze agents, antiskinning agents, pH adjusters, preservatives and the like can be blended into the main ingredient (I) and / or the hardener ingredient (II).

  Among them, examples of coloring pigments include titanium oxide, carbon black, yellow lead, yellow earth, yellow iron oxide, Hansaello, pigment yellow, chrome orange, chrome vermillion, permanent orange, amber, permanent red, brilliant carmine, fast violet And methyl violet lake, ultramarine blue, bitumen, cobalt blue, phthalocyanine blue, pigment green, naphthol green, aluminum paste and the like. These can be used alone or in combination of two or more.

  The compounding amount of the color pigment is suitably in the range of 5 to 90 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the resin non volatile matter contained in the aqueous coating composition.

  Examples of the extender pigment include talc, silica, calcium carbonate, mica, kaolin, barium sulfate and zinc oxide (zinc oxide). These can be used alone or in combination of two or more.

  The compounding amount of the extender pigment is 10 to 100 parts by mass, preferably 20 to 70 parts by mass, based on 100 parts by mass of the resin nonvolatile matter contained in the aqueous anticorrosion paint (B). Suitable from

"Organic solvent"
The aqueous anticorrosion paint (B) can contain an organic solvent. The organic solvent is used from the viewpoint of coating physical properties such as viscosity adjustment in the production of the main ingredient component (I) and / or the curing agent component (II) of the aqueous anticorrosion paint (B) or low temperature film forming property. As such an organic solvent, although known ones can be used without limitation, it is suitable to use the same compound as the organic solvent (a1) contained in the surface treatment liquid (A).

  The content of the organic solvent can be in the range of 0.1 to 30 parts by mass, preferably 3 to 25 parts by mass, based on 100 parts by mass of the resin non volatile matter contained in the aqueous anticorrosion paint (B).

  As a compounding ratio of the said main ingredient component (I) and hardening agent component (II), the functional group contained in the 2nd component is 0.3-1.5 to 1 equivalent of functional groups contained in the main ingredient component (I) It is suitable that it is in the range of equivalents, preferably 0.5 to 1.2 equivalents.

<Painting of aqueous anticorrosion paint (B)>
In the method of the present invention, when the aqueous anticorrosion paint (B) is applied, it is applied by diluting it with water such as deionized water or fresh water, if necessary. In this case, the non-volatile content concentration of the aqueous anticorrosion paint (B) is higher than that of the surface treatment liquid (A), and is preferably about 5 to 80% by mass, and about 35 to 75% by mass. More preferable.

  In the anticorrosion coating method of the present invention, the dry theoretical film thickness of the undercoat film formed by the aqueous anticorrosion paint (B) can be in the range of 10 to 200 μm, preferably 30 to 150 μm.

In the present invention, the dry theoretical film thickness is calculated by the following equation.
A = (B × NV) / (C × 100)
A: Theoretical dry film thickness (μm)
B: Coating amount (g / m ² )
NV: Non-volatile content concentration of paint (%)
C: Specific gravity of paint (g / cm ³ )
The specific gravity of the paint for determining the dry theoretical film thickness is to be measured in accordance with K 7232-1986 4.2 specific gravity cup method.

  The water-based anticorrosion paint (B) may be a conventionally known method such as air spray, airless spray, brushing, roller and the like. Moreover, as a drying method, it is desirable at normal temperature drying for 1 to 48 hours, preferably 2 to 16 hours, and it is also possible to carry out forced drying or heat drying as needed.

  In the anticorrosion coating method of the present invention, a top coat different from the aqueous anticorrosion paint (B) is formed in a single layer on the undercoat coating formed in the undercoat coating step (2) using the above aqueous anticorrosion paint (B). Alternatively, it can be applied in multiple layers.

Hereinafter, the present invention will be further described by way of examples. Here, "part" and "%" mean "mass part" and "mass%", respectively.

<Production of an organic solvent diluted water type surface treatment solution>
Production Example 1
In a container, 10 parts of isopropanol and 90 parts of deionized water were charged and mixed by stirring to obtain a surface treatment liquid (A-1).

Production Examples 2-5 and 7-12, 15
The surface treatment liquids (A-2) to (A-5), (A-7) to (A-12) and (A) are the same except that the type and amount of the organic solvent to be used are changed as described in Table 1. -15) was obtained.

<Manufacture of a surface treatment liquid of the type containing a water-based anticorrosion paint>
Production Example 6 and Production Examples 13 to 14
Base treatment liquids (A-6) and (A-13) in the same manner except using the aqueous anticorrosion paint (B-1) described later (a mixture of the main ingredient component and the curing agent ingredient component) in place of the organic solvent. And (A-14) were obtained.

<Production of amino group-containing resin emulsion>
Production Example 16
In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 3200 parts of “jER 828” (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A resin, epoxy equivalent 190, number average molecular weight 375), bisphenol A ( 1700 parts of molecular weight 228), 900 parts of methyl isobutyl ketone (boiling point 120 ° C.), and 5.0 parts of benzyldimethylamine were charged and reacted at 120 ° C. until the epoxy equivalent per nonvolatile matter became 2500 g / equivalent.

  Next, 590 parts of a ketimine compound of 3,3'-diaminodipropylamine with methyl isobutyl ketone was added and reacted at 120 ° C. for 1 hour. Thereafter, 54 parts of deionized water and 380 parts of glycidyl ester of neodecanoic acid were charged, and reacted at 100 ° C. for 2 hours. Thereafter, 90 parts of acetic acid and 70 parts of deionized water are added, and the inner solution is stirred and mixed, 6500 parts of deionized water is added and dispersed in water, and then the pressure is reduced to remove methyl isobutyl ketone. The fraction was adjusted to obtain a milky white, 45% non-volatile content, amino group-containing resin emulsion (BA-1) having a primary amino group at the resin end.

  The emulsion (BA-1) had a weight average molecular weight of resin of 7,000, an average particle size of 250 nm, and an amine value per nonvolatile component of 60 mg KOH / g.

Production Examples 17 to 20
Resin emulsions (BA-2) to (BA-5) were produced in the same manner except that the formulation was changed to the following Table 2.

<Manufacture of aqueous anticorrosion paint>
Production Example 21
In a container, 222 parts of amino group-containing resin emulsion (BA-1) (100 parts of non volatile matter), 10 parts of rust preventive pigment (b6-1), 10 parts of rust preventive pigment (b6-2), rust preventive pigment (b6- 7) 20 parts, 10 parts of fibrous inorganic compound (b7), 20 parts of ethylene glycol monobutyl ether (boiling point 171.2 ° C.), 40 parts of titanium oxide and 60 parts of talc are mixed and stirred to obtain a main ingredient component The In a separate container, add 35.2 parts (17.6 parts of non volatile matter), 5 parts of 2-ethylhexyl glycidyl ether, 7.5 parts of polycarbodiimide emulsion (3 parts of non volatile matter) to an epoxy resin emulsion (note), and stir The mixture was mixed to form a curing agent component, and mixed with the main component to obtain an aqueous anticorrosive paint (B-1).

Production Examples 22 to 26
Aqueous | water-based anticorrosion paints (B-2)-(B-6) were obtained like manufacture example 21 except setting a composition as Table 3 below.

  The compounding amounts of the amino group-containing resin emulsion, the epoxy group-containing resin emulsion and the polycarbodiimide emulsion in Table 3 are displayed as non-volatile components.

(*) Anticorrosion pigment (b6-1): “K-WHITE G-105” manufactured by Tayca, trade name, magnesium oxide-treated product of tripolyphosphate dihydrogen aluminum, magnesium oxide treated amount: 15%
(*) Anticorrosion pigment (b6-2): "LF Bowse MZP-500", trade name, manufactured by Kikuchi Color, magnesium phosphate,
(*) Antirust pigment (b6-3): "EXPERT NP-1000" manufactured by Toho Pigment Industries, Ltd., trade name, calcium phosphate,
(*) Antirust pigment (b6-4): Zinc phosphate tetrahydrate, manufactured by Yoneyama Pharmaceutical Co., Ltd., reagent, zinc phosphate,
(*) Antirust pigment (b6-5): "SHIELDEX C303" W. R. Grace & Co. Company name, calcium ion exchange silica,
(*) Anticorrosion pigment (b6-6): “Silo mask Mg” manufactured by Fuji Silysia Chemical Ltd., trade name, magnesium ion exchange silica,
(*) Antirust pigment (b6-7): “Silo mask 22 MR-H” manufactured by Fuji Silysia Chemical Ltd., trade name, magnesium ion exchange silica,
(*) Fibrous inorganic compound (b7): glass fiber, aspect ratio 20, average fiber length 80 μm,
(*) Epoxy resin emulsion (note): Nonionic phenol novolak type epoxy resin emulsion, nonvolatile content 50%, epoxy equivalent per nonvolatile content 200, weight average molecular weight 1200, average particle diameter 550 nm,
(*) Polycarbodiimide emulsion (b8): non volatile matter 40%, carbodiimide equivalent 365.

<Creating a test plate painted on a rusted surface>
Examples 1 to 23 and Comparative Examples 1 to 4
Assuming a rusted surface, shot blasting a 70 mm wide × 150 mm long × 3 mm thick mild steel plate onto the Pacific coast of Chikura-cho, Chiba Prefecture (off distance 30 m) for 4 months, with an angle of 30 ° south An open exposure test was carried out in S. to prepare a rusted steel plate having a rust generation area of 100%, and a rust steel plate having a rust generation area of 85% was prepared manually by using a wire brush. The surface treatment solutions and the aqueous anticorrosion paints obtained in the above-mentioned production examples were coated on this rusted steel plate to prepare a test plate, which was subjected to the following evaluation.
(*) On the entire surface of a 5 ° C. film-forming rust-proof steel plate, each surface treatment solution was coated with a nylon brush for water-based paint so as to obtain the coating amount shown in Table 4 and left at 5 ° C. for 5 minutes. Subsequently, each aqueous | water-based anticorrosion paint of Table 4 was mounted with nylon brush for water-based paints so that theoretical dry film thickness might be 100 micrometers, and it was made to dry at 5 degreeC for 24 hours, and the test plate was obtained. The surface condition of the obtained test plate was observed and evaluated according to the following criteria.
◎: The film-forming property is very good and no cracks occur
:: Good film forming property, and only slight slight cracks are observed at the end of the film,
Δ: film forming property, and although attached to the glass plate, cracks are observed in the whole,
X: No film formation, cracking occurs in the entire coating film, and peeling is observed in the coating film.
(*) Finger dry property In the above 5 ° C. film forming test, a test plate for finger dry property test is similarly prepared except that the drying temperature of the surface treatment solution and the aqueous anticorrosion paint is changed from 5 ° C. to 23 ° C. The stickiness was evaluated according to the following criteria in a state where the surface of each test plate was touched with a finger and rubbed back and forth.
◎: There is no stickiness and the coating does not peel even when rubbed with a finger,
:: There is slight stickiness, but it is immediately separated from the finger, and when rubbed with a finger, the coating slightly peels off, but can not be completely removed,
Δ: Stickiness is remarkable, and most of the coating can be removed by rubbing with a finger,
X: The coating film is broken and it can be easily removed by rubbing with a finger.
(*) Moisture resistance test A constant temperature and high humidity device was prepared at 50 ° C. × 98 RH% by preparing a test plate similar to the test plate for the above-mentioned finger dry property test except that the aqueous anticorrosion paint was dried for 168 hours after painting. The sample was suspended in a tank and allowed to stand for 120 hours, and then evaluated according to the following criteria.
:: The coated surface condition is very good, no blisters / rusts are recognized at all,
○: Good coating surface condition, slight blistering or rusting of 1 mm or less,
:: The coated surface condition is somewhat poor, and blisters or rust exceeding 1 mm are observed.
X: The coated surface condition is poor, and blistering or rusting is observed on the entire coated surface.

(*) Anticorrosion Test Each surface treatment liquid was coated with a nylon brush for water-based paint on the entire surface of a rusted steel plate so as to obtain the coating amount shown in Table 4, and stood upright at 23 ° C. for 3 minutes. The state of the simple substrate adjusting plate at this time was a deep wet color, and when the rusted surface was lightly touched with a finger, the finger was moistened by the surface treatment liquid soaked in the rust. Subsequently, each aqueous | water-based anticorrosion paint of Table 4 was painted with the nylon brush for water-based paints so that theoretical dry film thickness might be 100 micrometers, and it was made to dry at 23 degreeC for 24 hours. Next, the dry film thickness of the weak solvent soluble epoxy resin middle coat paint “CERATECTM Mild middle coat (E)” (trade name, Kansai Paint Co., Ltd., main agent / hardener mass ratio 17/1) is adjusted to 30 μm. And spray dried at 23 ° C. for 24 hours. Next, a low-pollution, weak solvent-soluble isocyanate-curable polyurethane resin topcoat “Ceratek U mild top coat” (trade name, Kansai Paint Co., Ltd., main agent / hardener mass ratio 6/1) to a dry film thickness of 25 μm It spray-painted, and it aged for 7 days in 23 degreeC and a 50% humidity constant temperature room, and obtained the test paint board painted on the rust surface. A composite cycle corrosion test using a 5% sodium chloride aqueous solution specified in JIS K 5621 was performed for 1200 hours on each of the test coated plates thus obtained, and the surface observation of the general part and the cut part of the test coated plate According to the following criteria, it evaluated.
(General)
◎: Occurrence of rust is not recognized,
○: Rust generation less than 5 mm in diameter of 1 to 5 points is observed in the test body,
Δ: 1 to 5 rusting was observed in the test body and 6 to 15 rusting was observed regardless of the size of rust exceeding 5 mm in size or rust size
X: Rust generation | occurrence | production of 15 points or more is recognized by the test body.
(Cut section)
:: The maximum width of rust and blister advancing from the cut portion is 10 mm or less across the cut,
○: The maximum value of rust and blister advancing from the cut part is more than 10 mm and less than 20 mm across the cut,
:: The maximum value of rust and blister advancing from the cut portion exceeds 20 mm and 30 mm or less across the cut,
X: The maximum value of rust and blister advancing from the cut portion exceeds 30 mm across the cut.

Claims (8)

The coating amount of the surface treatment solution (A) containing the organic solvent (a1) and water on the rust surface and the amount of the organic solvent (a1) in the total treatment solution is in the range of 0.1 to 65% by mass The surface treatment process (1) which is painted in the range of 50-550 g / m < ² >, is impregnated, and carries out the surface treatment of a rust surface,
An undercoating step (2) of applying an aqueous anticorrosion paint (B) to the surface treated part obtained in the step (1),
Anti-corrosion coating method of rust surface.   The anticorrosion coating method according to claim 1, wherein the aqueous anticorrosion paint (B) is applied after the surface treatment liquid (A) is applied and before complete drying.   The anticorrosive coating according to claim 1 or 2, wherein the surface treatment liquid (A) contains an aqueous anticorrosion paint (B) as a part of its components, and the non-volatile content concentration is in the range of 2 to 50%. Method.   The aqueous anticorrosion paint (B) is a two-component type, and the main component (I) contains an amino group-containing resin emulsion containing an epoxy resin and a polyamine compound as manufacturing raw materials, and a curing agent component (II) contains an epoxy group-containing resin emulsion The anticorrosive coating method according to any one of claims 1 to 3, which comprises   The anticorrosive coating method according to claim 4, wherein the amino group-containing resin emulsion uses a reactive group-containing softener capable of reacting with an amino group as a production raw material.   The anticorrosive coating method according to claim 4 or 5, wherein the weight average molecular weight of the resin of the epoxy group-containing resin emulsion is lower than the weight average molecular weight of the resin of the amino group-containing resin emulsion.   An anticorrosion pigment capable of eluting at least one ion selected from an aqueous anticorrosive paint (B) from magnesium ion, aluminum ion, calcium ion, zinc ion, silicate ion, phosphate ion, vanadate ion and molybdate ion The anticorrosion coating method according to any one of claims 1 to 6, which comprises (b6-1).   The coated article to which the anticorrosion coating of any one of Claim 1 thru | or 7 was given.