JP2019172783A - Water-based coating composition containing calcium hydroxide and/or magnesium hydroxide - Google Patents

Abstract

Kind Code: A1 Calcium hydroxide and / or magnesium hydroxide that can be easily produced, have excellent storage stability, coating workability, and finish of a coating film, and can form a coating film in which cracks and bumps are unlikely to occur. Providing an aqueous coating composition comprising: SOLUTION: It contains calcium hydroxide and / or magnesium hydroxide (A), carboxy group-containing dispersion resin (B), alkali metal compound (C), compound (D) having an amino group and an acid group, and water. An aqueous coating composition which may further contain a thickener and / or a binder resin (E), wherein the carboxy group-containing dispersion resin (B) and a compound (D) having an amino group and an acid group Wherein the alkali metal compound (C) is contained in the range of 0.1 to 2.0 mol per 1 mol of the acid group contained in the thickener and the binder resin (E). Paint composition. [Selection diagram] None

Description

  The present invention relates to an aqueous coating composition containing calcium hydroxide and / or magnesium hydroxide as a film-forming component, and a coated article having a coating film formed from the aqueous coating composition.

  Stucco and dolomite plaster have long been known as coating agents containing calcium hydroxide and magnesium hydroxide. These coating materials have excellent functions such as humidity control, antifungal properties, antibacterial properties, antiviral properties, deodorizing properties, formalin decomposability and fireproofing properties in addition to a calm and solid finish. Has been reviewed as a coating material for environmental improvement.

  However, the coating of plaster and dolomite plasters requires skilled personnel, and plaster and dolomite plasters after coating are prone to cracking during the drying process and cracks on the coating even after drying. Or sometimes peeled off.

  In order to compensate for these disadvantages, an aqueous composition containing a main component of plaster or dolomite plaster, which contains a natural or synthetic resin component, has been proposed. Such an aqueous composition may be expressed as an aqueous coating composition or an aqueous coating composition because the fluidity is improved by blending the resin component and roller coating or brush coating is possible.

  For example, Patent Document 1 proposes an aqueous coating composition containing slaked lime, a binder, and a polar amino acid. The aqueous coating composition can be applied without the skill of a skilled person, is excellent in the finish of the coating film, and does not easily crack the coating film. Therefore, the said aqueous coating agent has come to be applied also to the to-be-coated object which was difficult to coat | cover with the conventional plaster and dolomite plaster.

  On the other hand, due to the increasing awareness of environmental improvement in recent years, the antibacterial and antiviral functions of aqueous coating compositions containing slaked lime have become widely recognized, and not only the walls and ceilings of living rooms, but also a sense of quality and high design. The water-based coating composition has been applied to furniture and decorations that require high performance. Along with the application to these objects, the brittleness and adhesion are further improved, and the generation of cracks and blisters is further suppressed, etc., with respect to the coating film by the aqueous coating composition containing slaked lime. Has come to be required.

  In addition, although the above aqueous coating composition has significantly improved fluidity compared to plaster and dolomite plaster, the fluidity of the composition may change during storage, which may reduce the paint workability. Is required.

  Furthermore, the manufacture of the above-mentioned aqueous coating composition requires strict manufacturing process control in order to reduce the fluctuation width of the viscosity between manufacturing lots, but from the viewpoint of quality control, a composition that can be manufactured more easily is desired. It has been.

JP 2008-115376 A

  The object of the present invention is calcium hydroxide and / or that can be easily produced, has excellent storage stability, coating workability, and finish of the coating film, and can form a coating film that does not easily generate cracks or blisters. It is to provide an aqueous coating composition comprising magnesium hydroxide. Another object of the present invention is to provide a coated article having antibacterial and antiviral properties, which is coated and coated with the aqueous coating composition.

That is, in an exemplary embodiment, the present invention
Item 1. Contains calcium hydroxide and / or magnesium hydroxide (A), carboxy group-containing dispersion resin (B), alkali metal compound (C), compound (D) having an amino group and an acid group, and water. An aqueous coating composition that may contain a sticky agent and / or a binder resin (E),
The alkali metal compound (C) with respect to 1 mol of the acid group contained in the carboxyl group-containing dispersion resin (B), the compound (D) having an amino group and an acid group, the thickener and the binder resin (E). Is contained in the range of 0.1 to 2.0 mol.
Item 2. Item 2. The aqueous coating composition according to Item 1, wherein the acid value of the carboxy group-containing dispersion resin (B) is in the range of 4 to 400 mgKOH / g.
Item 3. Content of the said carboxy group containing dispersion resin (B) exists in the range of 0.5-15.0 mass parts with respect to a total of 100 mass parts of the said calcium hydroxide and / or magnesium hydroxide (A). Item 3. The water-based coating composition according to item 1 or 2.
Item 4. Furthermore, titanium white is included, The content is any one of claim | item 1 thru | or 3 which exists in the range of 20-150 mass parts with respect to a total of 100 mass parts of calcium hydroxide and / or magnesium hydroxide (A). The water-based coating composition according to item.
Item 5. Any one of Items 1 to 4, which contains a binder resin (E) and whose content is in the range of 10 to 100 parts by mass with respect to 100 parts by mass in total of calcium hydroxide and / or magnesium hydroxide (A). The water-based coating composition as described in any one of the above.
Item 6. The content of the compound (D) having an amino group and an acid group is 0.1 to 15.0 parts by mass with respect to a total of 100 parts by mass of the calcium hydroxide and / or magnesium hydroxide (A). Item 6. The aqueous coating composition according to any one of Items 1 to 5, which is within a range.
Item 7. The alkali metal compound with respect to 1 mol of the acid group contained in the carboxyl group-containing dispersion resin (B), the compound (D) having an amino group and an acid group, the thickener and the binder resin (E). Item 7. The aqueous coating composition according to any one of Items 1 to 6, wherein (C) is contained within a range of 0.2 to 1.5 mol.
Item 8. Item 8. The aqueous coating composition according to any one of Items 1 to 7, wherein the compound (D) having an amino group and an acid group contains a compound (D ′) having an amino group and a carboxy group.
Item 9. Item 9. A coating method in which the water-based coating composition according to any one of Items 1 to 8 is applied to an object to be coated.
Item 10. Item 9. A coated article obtained by coating the article to be coated with the aqueous coating composition according to any one of Items 1 to 8.
About.

  The water-based coating composition of the present invention can be easily produced, and can form a coating film that is excellent in storage stability, coating workability, and finish of the coating film, and is less prone to cracking and blistering.

Hereinafter, the aqueous coating composition of the present invention will be described in more detail.
In a typical embodiment, the aqueous coating composition of the present invention comprises calcium hydroxide and / or magnesium hydroxide (A), a carboxy group-containing dispersion resin (B), an alkali metal compound (C), an amino group and an acid group. A water-based coating composition containing a compound (D) having a water content and further containing a thickener and / or a binder resin (E), the carboxy group-containing dispersion resin (B), The alkali metal compound (C) is 0.1 to 2.0 mol per mol of the acid group contained in the compound (D) having an amino group and an acid group, the thickener and the binder resin (E). It is included within the range.

<Calcium hydroxide and / or magnesium hydroxide (A)>
Calcium hydroxide and / or magnesium hydroxide (A) exhibits functions such as antifungal, antibacterial, antiviral, deodorant, and humidity control properties of the coating film obtained by the aqueous coating composition of the present invention. It is a component to do. Hereinafter, “calcium hydroxide and / or magnesium hydroxide (A)” may be referred to as “component (A)”.

  In addition, the component (A) not only plays a role of giving the resulting coating a calm and heavy finish, but also gives physical strength to the coating by reaction with carbon dioxide in the atmosphere on the coating surface. It also has a role. In order for the obtained coating film to fully exhibit the above functions and roles attributable to the component (A), the component (A) is based on the total solid content contained in the aqueous coating composition of the present invention. Is preferably contained within the range of 70 to 20% by mass, and more preferably within the range of 60 to 30% by mass.

  When the blending amount of the component (A) is less than 20% by mass, the excellent functions (antifungal property, antibacterial property, deodorant property, humidity control property) due to calcium hydroxide or magnesium hydroxide cannot be sufficiently exhibited. In addition, there may be a lack of calm and solid finish. Moreover, when more than 70 mass%, the storage stability and coating workability | operativity of the obtained water-based coating composition may fall.

  The said calcium hydroxide can use what is industrially produced as calcium hydroxide or slaked lime. In the present specification, “calcium hydroxide” may be referred to as “slaked lime”. Calcium hydroxide can be manufactured using limestone as a raw material, but may be manufactured using a shell, shell, egg shell, animal bone, or the like as a raw material. As a raw material for producing the aqueous coating composition of the present invention, one containing calcium hydroxide as a main component may be used, for example, one containing calcium carbonate, quicklime, magnesium hydroxide, magnesium oxide or the like as other components, An impurity containing oxides such as iron, aluminum, phosphorus, or silica may be used as a manufacturing raw material.

  The said magnesium hydroxide can use what is produced industrially. As an industrial raw material containing magnesium hydroxide, dolomite hydroxide may be used. Hydroxide dolomite is generally produced by the reaction of light-burned dolomite and water, and contains calcium hydroxide and magnesium hydroxide as main components. Although the component ratio of calcium hydroxide and magnesium hydroxide may differ depending on the production area and manufacturing process of dolomite, for example, 63:37 (mass ratio) hydroxide dolomite can be used.

  The aqueous coating composition of the present invention can contain calcium hydroxide and magnesium hydroxide in any proportion. When blending slaked lime as a raw material, magnesium hydroxide may not be substantially contained. Moreover, when mix | blending slaked lime and dolomite hydroxide as a raw material, content of magnesium hydroxide is 0.1-40 with respect to the total mass of calcium hydroxide and magnesium hydroxide contained in an aqueous coating composition. You may adjust within the mass% range.

<Carboxy group-containing dispersion resin (B)>
The carboxy group-containing dispersion resin (B) in the present invention is intended to ensure the dispersion of the component (A) and the good storage stability, coating workability, finish, etc. of the aqueous coating composition of the present invention. Used as

  As long as the carboxy group-containing dispersed resin (B) has a carboxy group, the type and structure of the resin are not limited. Examples of the carboxy group-containing dispersion resin (B) include acryl group-containing acrylic resins, polyurethane resins, polyolefin resins, polyester resins, alkyd resins, epoxy resins and the like, modified resins of these resins, and any two A composite or a mixture of two or more kinds of resins can be mentioned. In addition, the carboxy group-containing dispersion resin (B) is structurally composed of random copolymers, block copolymers, graft copolymers, gradient copolymers, dendrimers, branched polymers, hyperbranched polymers, telechelic polymers, polymers having a functional group at one end, and the like. It may be classified.

The acid value of the carboxy group-containing dispersion resin (B) is not limited, but is, for example, in the range of 4 to 400 mgKOH / g, preferably 7 to 300 mgKOH / g, and more preferably 8 to 250 mgKOH / g. Here, the acid value is obtained by determining the number of mg of potassium hydroxide necessary for neutralizing the acidic free functional group contained in 1 g of the resin by a conventional method based on alkali neutralization titration. When the acid value of the carboxy group-containing resin (B) is less than 5 mgKOH / g, the storage stability of the obtained aqueous coating composition may be inferior, and the resulting coating film may be fuzzy. is there. When this acid value is larger than 400 mgKOH / g, the viscosity of the obtained aqueous coating composition may become high. Further, the hydroxyl value of the carboxy group-containing dispersion resin (B) is not limited, but is preferably 450 mgKOH / g or less. The measurement of a hydroxyl value can be performed based on JISK-0070 (1992). Specifically, 5 ml of acetylating reagent (acetic anhydride pyridine solution adjusted to 100 ml by adding pyridine to 25 g of acetic anhydride) was added to the sample, heated in a glycerin bath, and then added with potassium hydroxide solution. It can be titrated with phenolphthalein as an indicator and calculated by the following formula.
Hydroxyl value (mgKOH / g) = [V × 56.1 × C / m] + D
V: titer (ml),
C: concentration of titrant (mol / l),
m: solid content mass (g) of the sample, D: acid value of the sample (mgKOH / g).

  Further, the weight average molecular weight of the carboxy group-containing dispersion resin (B) is not limited, but is, for example, 1,000 to 100,000, preferably 2,000 to 80,000, and more preferably 3,000 to 45,000. Is within the range. When the weight average molecular weight is less than 1000, the storage stability of the aqueous coating composition of the present invention may be inferior, and the resulting coating film may be fuzzy. On the other hand, when the weight average molecular weight is larger than 100,000, the viscosity of the aqueous coating composition of the present invention may be increased.

  In the present specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), and can be measured under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. it can.

  The blending amount of the carboxy group-containing dispersion resin (B) is not limited, but is, for example, 0.5 to 15.0 mass%, preferably 0.7 to 12.0 mass%, based on the mass of the component (A). More preferably, it exists in the range of 1.0-10.0 mass%.

  When the blending amount of the carboxy group-containing dispersion resin (B) is less than 0.5% by mass, the storage stability of the obtained water-based coating composition may be inferior, and the resulting coating film is flawed. There are things to do. When there are more compounding quantities of carboxy-group containing resin (B) than 15 mass%, the viscosity of an aqueous coating composition may become high.

  Although there is no restriction | limiting in particular in the kind of carboxy group containing dispersion resin (B), At least 1 sort (s) chosen from the group which consists of an acrylic resin (b-1), polyolefin resin (b-2), and a polyurethane resin (b-3). Is preferably used.

  As the acrylic resin (b-1), a carboxy-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers copolymerizable with the carboxy group-containing polymerizable unsaturated monomer are generally known per se, For example, it can be produced by copolymerization by a method such as a solution polymerization method using a polymerization initiator in an organic solvent. As the polymerization initiator, a known polymerization initiator such as an azo compound, a peroxide, or a metal compound may be used. In the polymerization reaction, a chain transfer agent may be used as necessary. The structure of the acrylic resin (b-1) may be any of a random copolymer, a block copolymer, a graft copolymer, a gradient copolymer, etc., and can be produced by a known polymerization method. . In addition, when manufacturing an acrylic resin (b-1) by the solution polymerization method, you may use after removing a solvent.

  Examples of the carboxy-containing polymerizable unsaturated monomer include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, and (meth) acrylic acid β-carboxyethyl. Examples thereof include carboxyl group-containing monomers.

  On the other hand, examples of other polymerizable unsaturated monomers copolymerizable with the carboxy group-containing polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate or other alkyl or Alkyl (meth) acrylates having an alkyl group such as cycloalkyl (meth) acrylate; aromatic ring-containing polymerizable unsaturated monomers such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene; 2-hydroxyethyl (meta ) (Meth) acrylic acid such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-8 carbon atoms Monoesterified product with dihydric alcohol, ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms, N-hydroxymethyl (meth) acrylamide, allyl alcohol, Hydroxyl group-containing polymerizable unsaturated monomer such as (meth) acrylate having a polyoxyethylene chain whose molecular end is a hydroxyl group; (meth) acrylic acid dimethylaminoethylmethyl chloride salt, (meth) acrylic acid dimethylaminoethylbenzyl chloride salt, (Meth) acrylic acid diethylaminoethylmethyl chloride salt, (meth) acrylic acid diethylaminoethylbenzyl chloride salt, (meth) acrylic acid aminopropyldimethylammonium methyl chloride salt, (meth) acrylic acid aminopropyldimethylammonium ben Lucyl salt, aminopropyl diethylammonium methyl chloride (meth) acrylate, aminopropyl diethylammonium benzyl chloride (meth) acrylate, trimethylammonium methyl sulfate (meth) acrylate, triethylammonium methyl sulfate (meth) acrylate Salt, aminopropyldimethylammonium methylsulfate (meth) acrylate, aminopropyldimethylammonium ethylsulfate (meth) acrylate, trimethylaminoethyl p-toluenesulfonate (meth) acrylate, aminopropyldimethyl (meth) acrylate Quaternary ammonium group-containing polymerizable unsaturated monomers such as ethylammonium ethyl sulfate salt; vinyltrimethoxysilane, vinyltrie Polymerizable unsaturated monomers having alkoxysilyl groups such as toxisilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutyl Perfluoroalkyl (meth) acrylates such as ethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; polymerizable unsaturated monomers having fluorinated alkyl groups such as fluoroolefins; and photopolymerizable functional groups such as maleimide groups Polymerizable unsaturated monomers having: N-vinyl pyrrolidone, ethylene, propylene, isoprene, butadiene, chloroprene, vinyl propionate, vinyl acetate and other vinyl compounds; (meth) acrylonitrile, (meth) acrylamid Nitrogen-containing polymerizable unsaturated monomers such as N; methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, Alkoxy group-containing polymerizable unsaturated monomers such as alkoxyalkyl (meth) acrylates such as ethoxypropyl (meth) acrylate and polyalkylene glycol monoalkoxy (meth) acrylates such as polyethylene glycol monomethoxy (meth) acrylate; polyethylene glycol mono (meta ) Monoesterified product of (meth) acrylic acid such as acrylate and polyalkylene glycol; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetate Examples thereof include carbonyl group-containing polymerizable unsaturated monomers such as ciethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc. Can be used alone or in combination of two or more.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means acrylamide or methacrylamide.

  As the polyolefin resin (b-2), a known carboxy group-containing polyolefin resin can be used. For example, a polyolefin resin modified with a carboxy group-containing unsaturated compound, and an olefin monomer and a carboxy group-containing polymerizable resin. Examples thereof include carboxy group-containing polyolefin resins such as copolymers with saturated monomers.

  As said polyurethane resin (b-3), what was obtained by the polyaddition reaction of polyisocyanate and a carboxy-group containing polyol can be mentioned, for example.

<Alkali metal compound (C)>
Examples of the alkali metal compound (C) include compounds of alkali metals such as lithium, sodium, potassium, rubidium, cesium, and francium. Specific examples of the alkali metal compound (C) include hydroxides, alkoxylates, oxides, halides, salts with organic groups having a carboxy group, and the like. The hydroxide is preferred.

  The alkali metal compound (C) is a carboxy group-containing dispersion resin (B), a compound (D) having an amino group and an acid group, a thickener and a binder resin (E) (thickener and component (E)). In the case where these components are contained in the coating composition), in the range of 0.1 to 2.0 mol, preferably in the range of 0.2 to 1.5 mol, per 1 mol of all acid groups contained in the coating composition By containing in, the storage stability of the obtained water-based coating composition is improved, the irregularities generated in the obtained coating film can be greatly suppressed, and the water-based coating composition can be easily produced. Can do. When the blending amount of the alkali metal compound (C) is less than 0.1 mol with respect to 1 mol of the acid group, the storage stability of the obtained aqueous coating composition may be insufficient. When the amount is more than the above, the water resistance of the coating film may be impaired.

  As long as the aqueous coating composition of the present invention contains the alkali metal compound (C) within the above range, other basic compounds such as organic amine compounds such as triethylamine and dimethylaminoethanol, ammonia, and quaternary ammonium compounds. Etc. may be included.

<Compound (D) having an amino group and an acid group>
By blending the compound (D) having an amino group and an acid group, the aqueous coating composition of the present invention can be easily produced, and the storage stability of the obtained aqueous coating composition is improved. Cracks and blisters generated in the coated film can be greatly suppressed.

  Although the compounding quantity of the said compound (D) is not limited, For example, 0.1-15.0 mass parts with respect to a total of 100 mass parts of the said calcium hydroxide and / or magnesium hydroxide (A), Preferably It is 0.2-12.0 mass parts, More preferably, it exists in the range of 0.5-10.0 mass parts. When the compounding amount of the compound (D) is less than 0.1 parts by mass, the cracks and blisters generated in the coating film may not be sufficiently suppressed. When the compounding amount is more than 15.0 parts by mass, the obtained coating film Tack may remain on the surface.

  In the compound (D) having an amino group and an acid group, examples of the acid group include a carboxy group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group.

  Among the compounds having a carboxy group as the acid group among the compounds (D), specifically, glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, Methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, theanine, tricolominic acid, kainic acid, cystine, hydroxyproline, hydroxylysine, thyroxine, phosphoserine, desmosine, β-glycine, β-alanine, sarcosine, N- Methylglycine, ornithine, citrulline, creatine, γ-aminobutyric acid, opain, trimethylglycine, 7-aminoheptanoic acid, 6-aminohexanoic acid, 12-aminolauric acid, 5-amino Amino acids such as pentanoic acid and aminobenzoic acid; polymers of the above amino acids (dipeptides, tripeptides, oligopeptides, polypeptides, etc.); nitrile triacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), ethylenediaminesuccinic acid, diethylenetriaminopenta Acetic acid (DTPA), triethylenetetramine hexaacetic acid (TTHA), L-glutamic acid diacetic acid (GLDA), L-aspartic acid diacetic acid (ASDA), 1,3-propanediaminetetraacetic acid (PDTA), dimercaptor succinate Acid (DMSA) and methylglycine diacetic acid (MGDA), dihydroxyethylglycine (DEG), triethanolamine (TEA), N- (2-hydroxyethyl) iminodiacetic acid (HEIDA), hydroxyethylethylenediaminetriacetic acid (HEDTA) ), Dihydroxyethylethylenediaminediacetic acid (DHEDDA) and 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), bis (2-aminoethyl) ethylene glycol tetraacetic acid, triethylenetetraminehexaacetic acid, trans-1, Mention may be made of aminocarboxylic acids such as 2-diaminocyclohexanetetraacetic acid. Examples of the compound (D) having a sulfonic acid as an acid group include taurine, N-methyltaurine, hypotaurine, 5-amino-1-pentanesulfonic acid, 2- (butylamino) ethanesulfonic acid, 3- Examples include aminobenzene sulfonic acid and 4-aminobenzene sulfonic acid. Examples of the compound (D) having sulfinic acid as an acid group include 3-amino-1-propanesulfinic acid and 1-amino-2-propanesulfinic acid. Among the compounds (D), compounds having phosphonic acid as an acid group include 2-aminoethylphosphonic acid, aminophenylphosphonic acid, 3-aminopropylphosphonic acid, 4-aminobutylphosphonic acid, and 2- (methylamino) ethyl. Examples include phosphonic acid, 1-aminobutylphosphonic acid, and 1-aminoethylphosphonic acid. Examples of the compound having phosphinic acid as an acid group in the compound (D) include methyl (3-aminopropyl) phosphinic acid, (2-aminoethyl) phosphinic acid, butyl (3-aminopropyl) phosphinic acid and the like. Of these, compounds having a carboxy group as the acid group are preferred.

<Pigment>
The aqueous coating composition of the present invention may contain a color pigment or an extender pigment. By blending titanium white as the color pigment, the concealability of the obtained coating film is improved and uneven coating can be suppressed. The titanium white may be any crystal type of rutile type, anatase type, and brookite type. The titanium white may be produced by any method such as chlorine method or sulfuric acid method. The titanium white may be surface-treated with an oxide of a metal such as aluminum, zirconium or silicon, or a calcium phosphate compound such as hydroxyapatite.

  As the titanium white, those having an average particle diameter in the range of 10 nm to 1500 nm are preferably used, and those having an average particle diameter in the range of 150 nm to 500 nm are preferable from the viewpoint of the coloring power and finish of the coating film. Can be used. Here, the average particle diameter of the titanium white pigment is an average particle diameter measured by observation with an electron microscope. Since titanium white pigment is substantially spherical, the diameter is measured. Specifically, 100 particles are selected from the transmission electron microscope image, and the average particle diameter is obtained using NIH Image 1.63 free software manufactured by NIH (National Institute of Health).

  Although the compounding quantity of the said titanium white is not limited, For example, from a viewpoint of concealment property, 150 mass parts or less with respect to a total of 100 mass parts of calcium hydroxide and / or magnesium hydroxide (A), Preferably 20- It is 150 mass parts, More preferably, it exists in the range of 25-125 mass parts. By blending titanium white within the above range, the concealment of the coating is improved and it is effective in suppressing uneven coating, and coloring and color stability when mixed with colors other than white are good. can do.

  Examples of white pigments other than titanium white include zinc oxide, zinc carbonate, zinc sulfide, lithopone, lead sulfate, lead white, antimony oxide, aluminum nitride, boron nitride, and zirconium oxide. Even if it uses individually by 1 type, it can also be used in combination of 2 or more type.

  As the colored pigments other than white, any of organic pigments and inorganic pigments may be used, for example, complex oxide pigments, carbon black, iron oxide pigments, red lead, vermilion, ultramarine, chrome yellow, cadmium yellow. , Zinc chromate, cadmium red, azo pigment, diketopyrrolopyrrole pigment, perylene pigment, perinone pigment, quinacridone pigment, isoindolinone pigment, benzimidazolone pigment, phthalocyanine pigment, isoindoline pigment , Metal chelate azo pigments, indanthrone pigments, dioxazine pigments, selenium pigments, indigo pigments, bitumen and the like, and these can be used alone or in combination of two or more.

  Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white.

<Binder resin (E)>
The water-based coating composition of the present invention can be blended with the binder resin (E) from the viewpoints of improving the coating workability, improving the adhesion of the coating film to the object to be coated, and suppressing cracking.

  The acid value of the binder resin (E) is preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, from the viewpoint of storage stability. When the acid value is larger than 60 mgKOH / g, the storage stability and coating workability of the obtained water-based coating composition may be deteriorated, or the adhesion to an object to be coated may be deteriorated.

  Although the compounding quantity of binder resin (E) is not limited, For example, 100 mass parts or less with respect to a total of 100 mass parts of the said calcium hydroxide and / or magnesium hydroxide (A), Preferably 10-100 mass parts More preferably, it is in the range of 20 to 70 parts by mass. When the amount is more than 100 parts by mass, the functions such as antifungal property, antibacterial property, deodorant property and humidity control attributed to calcium hydroxide and magnesium hydroxide may not be sufficiently exhibited, There may be a lack of a solid finish feeling.

  As the binder resin (E), any of a natural resin and a synthetic resin may be used as long as it can be used for the aqueous coating composition of the present invention.

  Examples of the natural resin include polysaccharides, starch, natural rubber, protein, gelatin, casein, polyglutamic acid, xanthan gum, hyaluronic acid, cellulose, resins extracted from seaweed, and the like. A modified one may be used.

  Examples of the synthetic resin include polyvinyl alcohol, polyoxyalkylene, polyolefin resin, polyamide resin, acrylic resin, polyurethane resin, alkyd resin, silicon resin, fluorine resin, epoxy resin, polyester resin, alkyd resin, polyether resin, poly Examples thereof include vinyl chloride resin, polybutadiene, and modified resins or composite resins of these resins. These natural resins and synthetic resins can be used singly or in combination of two or more.

  The binder resin (E) is preferably a water-soluble or water-dispersed resin. Examples of the water-solubilized resin include those obtained by introducing a hydrophilic group such as a carboxy group or a polyoxyethylene group into the resin by a known method. Examples of the water-dispersed resin include those obtained by a known method such as an emulsion polymerization method, a dispersion polymerization method, a method by water dispersion using a dispersant or an emulsifier.

  From the viewpoint of the coating workability of the aqueous coating composition of the present invention, and the adhesion of the coating film and the suppression of cracking, the binder resin (E) is an acrylic resin (e-1), a polyolefin resin (e-2), a polyurethane. The resin (e-3) and at least one selected from the group consisting of a composite resin (e-4) having two or more types of resins selected from these resins as constituent components are preferred.

  As the binder resin (E), in particular, from the viewpoint of coating film adhesion and crack suppression, for example, a resin having a weight average molecular weight of 10,000 or more, preferably 21,000 or more, more preferably 50,000 or more is used. be able to. The binder resin (E) may be either water-soluble or water-dispersible resin. The binder resin (E) may be water-dispersible crosslinked resin particles.

  As the acrylic resin (e-1), a water-soluble acrylic resin or a water-dispersible acrylic resin can be used. The water-soluble acrylic resin can be produced, for example, by solution polymerization. Moreover, a water-dispersible acrylic resin can be manufactured by polymerization methods, such as emulsion polymerization, miniemulsion polymerization, suspension polymerization, for example.

  Examples of the polymerizable unsaturated monomer that can be used for the polymerization include the same as those mentioned as the polymerizable unsaturated monomer that can be used for the production of the acrylic resin (b-1). In addition, if necessary, a monomer having two or more polymerizable unsaturated groups in the same molecule or a polymerizable unsaturated monomer having a functional group capable of reacting with itself or complementary to form a chemical bond is used. May be.

  The emulsion polymerization, miniemulsion polymerization and suspension polymerization can be carried out by conventional methods. Specifically, the emulsion polymerization can be performed by emulsion polymerization of a mixture of polymerizable unsaturated monomers in water using a surfactant and / or a dispersion resin and a polymerization initiator.

  In the emulsion polymerization, emulsion particles having a multilayer structure of two or more layers such as a core / shell type, emulsion particles having a gradient in the concentration distribution of the constituent monomer composition from the particle center toward the particle outer periphery, etc. Can be produced by a known method.

  As the polyolefin resin (e-2), a water-soluble or water-dispersible polyolefin resin known in the art can be used. Examples of the polyolefin resin include a carboxy group-containing polyolefin resin. Specifically, a polyolefin resin modified with a carboxy group-containing unsaturated compound, and a copolymer of an olefin monomer and a carboxy group-containing polymerizable unsaturated monomer. A polymer etc. can be mentioned.

  Examples of the olefin monomer constituting the carboxy group-containing polyolefin resin include ethylene, propylene, and α-olefins such as 1-butene, 1-hexene, and 1-octene.

  In the aqueous coating composition of the present invention, for example, a copolymer of ethylene and (meth) acrylic acid, a polyolefin resin obtained by modifying a polyolefin resin produced by a known method with maleic anhydride, and the like are preferably used. it can.

  As the polyurethane resin (e-3), those known in the art can be used. For example, by dispersing a urethane prepolymer obtained by reacting a polyisocyanate, a polyol and a carboxyl group-containing diol in water. Mention may be made of the resulting emulsion. Examples of the polyol include polyols such as polyester polyol, polycarbonate polyol, and polyether polyol, and low molecular weight polyols such as ethylene glycol and glycerin. In addition, the urethane prepolymer dispersed in water may be used as a polyurethane resin (e-3) as it is, but if necessary, at least two active hydrogens are contained in one molecule such as diol and diamine. You may use as a polyurethane resin (e-3) what is obtained by using the compound which has as a chain extender, and making it react further and performing chain extension reaction.

  Examples of the composite resin (e-4) include a composite resin of an acrylic resin and a polyurethane resin, a composite resin of an acrylic resin and a polyolefin resin, a composite resin of a polyurethane resin and a polyolefin resin, an acrylic resin, a polyolefin resin, and a polyurethane. Examples thereof include composite resins with resins. The composite resin means a resin in which different types of resins constituting the composite resin are chemically bonded to each other by a covalent bond, an ionic bond, a hydrogen bond, a hydrophobic bond, a van der Waals force, a metal bond, or the like. As the composite resin (e-4), those known in the art can be used.

<Other ingredients>
In addition to the above components, the aqueous coating composition of the present invention, if necessary, chelating agent, organic solvent, plasticizer, antifoaming agent, thickener, aggregate, resin beads, antirust pigment, surface conditioner, Silane coupling agents, emulsifiers, dispersants, water repellents, wetting agents, photocatalysts, ethylene urea, graphene, carbon nanotubes, nanocellulose, and the like may be blended. The aqueous coating composition of the present invention may contain a monovalent carboxylic acid such as acetic acid, a polyvalent carboxylic acid such as oxalic acid, and the like within the range in which the effects of the present invention are obtained.

  In another embodiment, the present invention relates to calcium hydroxide and / or magnesium hydroxide (A), a carboxy group-containing dispersion resin (B), an alkali metal compound (C), a compound having an amino group and a carboxy group (D '), And an aqueous coating composition containing water and further containing a thickener and / or binder resin (E), wherein the carboxy group-containing dispersion resin (B), amino group and carboxy group The alkali metal compound (C) is added in an amount of 0.1 to 2.0 mol (preferably 0.001 mol) with respect to 1 mol of the carboxy group contained in the compound (D ′), the thickener and the binder resin (E). 2 to 1.5 mol) of an aqueous coating composition; coating the aqueous coating composition on an object to be coated; a coating method; and applying the aqueous coating composition to an object of coating Paint Goods are also provided. Each component, blending amount, and the like of the coating composition in the embodiment includes the component (D ′), the blending amount of the component (C), the component (B), the component (D ′), the thickener, and the like. What was illustrated about the above-mentioned embodiment can be similarly employ | adopted except the point adjusted based on 1 mol of carboxy groups contained in a component (E).

  The coating composition of the present invention can be produced by mixing and stirring the above components. The preparation method and the stirring method can be appropriately selected depending on the blending composition and production scale. Moreover, you may manufacture in nitrogen atmosphere as needed.

<Painting and workpieces>
The aqueous coating composition of the present invention can be applied by a known coating method. Specific examples include dip coating, brush coating, flow coating, trowel coating, roller coating, spray coating, airless spray coating, flow coater coating, roll coater coating, and vacuum coater. Depending on the coating method and the object to be coated, the water-based coating composition of the present invention is prepared by adding water or an organic solvent to adjust the concentration, and adding a thickener or combining different types of thickeners. By blending, etc., the rheology of the aqueous coating composition can be appropriately prepared and applied.

  The solid content concentration of the aqueous coating composition of the present invention is preferably in the range of 40 to 65% by mass from the viewpoint of storage stability. In addition, solid content can be calculated | required as a heating residue which is the mass fraction of the residue obtained by evaporation under the predetermined conditions prescribed | regulated to JISK5601.

  The dry film thickness may be set as desired. For example, the coating composition of the present invention can be applied so as to have a thickness of about 1 μm to 10,000 μm.

  The aqueous coating composition of the present invention coated on the surface of the object to be coated may be dried by any method such as a natural drying method, a ventilation drying method, a reduced pressure drying method, a forced drying method or a heat drying method. When the coating composition is a paper, fiber, porous material, etc., after the water-based coating composition of the present invention is impregnated into the above material, a drying method is selected according to the properties of the coating material. Can be dried. In addition, the dry state of the coating film obtained by the said drying method may be any state of finger touch drying, semi-curing drying, and curing drying specified in JIS K5600-1-1. The above drying does not mean the degree of reaction between calcium hydroxide or magnesium hydroxide and carbon dioxide in the obtained coating film.

  The water-based paint composition of the present invention is a known paper such as paper, Japanese paper, cardboard, inorganic materials such as cement, concrete, mortar, gypsum, wood, synthetic resin, nonwoven fabric, fabric, fiber, organic inorganic composite material, etc. It can be applied to materials and can be applied to cloths, boards, panels, sheets, bags, etc. made from these materials. More specific objects to be coated include, for example, building walls and ceilings, joinery, curtains, carpets, tapestries, magnet sheets, chair upholstery, bedding, pillow covers, insoles, masks, aprons, clothes, Examples thereof include furniture such as lockers, chests, drawers, trash cans, bookcases and clogs, water supply products, partitions, air conditioners or air purifier filter members and air flow path members. Since the coating film obtained from the aqueous coating composition of the present invention has functions such as humidity control, antifungal properties, antibacterial properties, antiviral properties, deodorizing properties, and formalin degradability, hygiene and environmental improvement are required. The water-based coating composition of the present invention can be used for houses, public facilities, warehouses, barns and poultry facilities, disaster shelters, temporary tents, toilet articles, and the like. Moreover, you may utilize the bag and sheet | seat which apply | coated this invention and the aqueous coating composition for processing of food industry waste, excrement, vomit, a dead body, etc.

  The aqueous coating composition of the present invention can be directly applied to the article to be coated. However, dust and dirt attached to the article to be coated may be removed in advance before painting. Moreover, after applying a sealer, a primer, a rust preventive paint, etc. to the surface of a to-be-coated object, and forming an under_coat_film, you may apply the water-based coating composition of this invention.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass.

<Production of carboxy group-containing dispersion resins (b-1) to (b-4)>
Production Example 1
After charging 100 parts of propylene glycol monomethyl ether under atmospheric pressure into a 1000 ml pressurized reaction vessel equipped with a heating device, the reaction vessel was sealed and the internal liquid phase temperature was maintained at 200 ° C. while stirring at 200 rpm. In this state, a monomer mixture containing 30 parts of styrene, 32 parts of 2-ethylhexyl acrylate, 38 parts of acrylic acid, and 1 part of di-t-amyl peroxide was fed into the reaction vessel over 5 hours. The internal liquid phase temperature was maintained at 200 ° C. for 1 hour after the supply of the monomer mixture was completed, and then cooled to room temperature. The contents were transferred to another reaction vessel, and the volatile substance inside the reaction vessel was distilled off while reducing the pressure at a temperature of about 120 to 170 ° C. while stirring to obtain a carboxy group-containing dispersion resin (b-1). . The weight average molecular weight (hereinafter referred to as Mw) of the carboxy group-containing dispersed resin (b-1) was 7900, and the acid value was 296 mgKOH / g.

Production Examples 2 to 4
Except for the composition of the monomer mixture shown in Table 1 below, in the same manner as in Production Example 1, carboxy group-containing dispersion resins (b-2) to (b-4) of Production Examples 2 to 5 were obtained.

<Manufacture of binder resin>
Production Example 5
Production of Acrylic Resin (e-1a) An aqueous dispersion of core / shell type acrylic resin was produced by emulsion polymerization as follows.

  A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen inlet tube and dropping device, 128 parts of deionized water, and “ADEKA rear soap SR-1025” (trade name, manufactured by ADEKA, emulsifier, effective (Component 25%) 2 parts were charged, stirred and mixed in a nitrogen stream, and heated to 80 ° C.

  Next, 1% of the total amount of the following monomer emulsion for core part and 5.3 parts of 6% ammonium persulfate aqueous solution were introduced into the reaction vessel and kept at 80 ° C. for 15 minutes. Thereafter, the remainder of the monomer emulsion for the core part was dropped into a reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after completion of the dropping. Next, the following monomer emulsion for shell part was added dropwise over 1 hour, and after aging for 1 hour, it was cooled to 30 ° C. while gradually adding 40 parts of 5% 2- (dimethylamino) ethanol aqueous solution to the reaction vessel, The mixture was discharged while being filtered through a 100 mesh nylon cloth to obtain an aqueous dispersion of an acrylic resin (e-1a) having an average particle diameter of 100 nm and a solid content of 30%. The obtained acrylic resin aqueous dispersion had an acid value of 20 mgKOH / g and a hydroxyl value of 25 mgKOH / g. This acrylic resin (e-1a) was not able to measure the molecular weight because the inside of the dispersion particles was crosslinked using methylene bisacrylamide as a monomer.

  Monomer emulsion for core part: 40 parts of deionized water, 2.8 parts of “ADEKA rear soap SR-1025”, 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 of ethyl acrylate The monomer emulsion for the core part was obtained by mixing and stirring the part and 21 parts of n-butyl acrylate.

  Monomer emulsion for shell part: 17 parts of deionized water, 1.2 parts of “ADEKA rear soap SR-1025”, 0.03 part of ammonium persulfate, 3 parts of styrene, 5.1 parts of 2-hydroxyethyl acrylate, 3 parts of methacrylic acid .1 part, 8.0 parts of methyl methacrylate, 1.8 parts of ethyl acrylate and 9.0 parts of n-butyl acrylate were mixed and stirred to obtain a monomer emulsion for shell part.

Production Example 6
Production of polyurethane resin (e-3a) Polytetramethylene glycol (number average molecular weight 1000) 211.9 in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping device. 11.5 parts of α, α-dimethylolpropionic acid, 6.9 parts of trimethylolpropane, 112.2 parts of isophorone diisocyanate and 298.5 parts of methyl ethyl ketone, and the reaction system was replaced with nitrogen gas. The reaction was carried out at 80 ° C. to obtain an NCO-terminated urethane prepolymer having a free isocyanate group content of 3.2%. The obtained methyl ethyl ketone solution was cooled to 40 ° C., 493.2 g of deionized water containing 5.2 parts of triethylamine was added and emulsified, and then 159.2 parts of 5% ethylenediamine aqueous solution was added thereto, followed by stirring for 60 minutes, and then methyl ethyl ketone. Was distilled off under reduced pressure and the concentration was adjusted with deionized water to obtain an aqueous dispersion of a polyurethane resin (e-3a) having a solid content of 35%, an acid value of 14 mgKOH / g, and an average particle size of 120 nm. This urethane resin (e-3a) could not be measured for molecular weight because the dispersion particles were crosslinked inside.

Preparation of paint (water-based paint composition (S-1) to (S-37))
Example 1
100 parts of calcium hydroxide, 5.0 parts of the carboxy group-containing resin (b-2) obtained in Production Example 2, 0.85 parts of potassium hydroxide, 1.50 parts of glycine, Newcol 707 (Note 3): 1 Part, SN deformer 777 (Note 4): 2 parts, HEC AL-15F (Note 5): 1 part, and water are dispersed and mixed in a container equipped with a stirrer to form an aqueous coating composition having a solid content of 52% A product (S-1) was obtained.

Example 2
100 parts of calcium hydroxide, 5.0 parts of carboxy group-containing resin (b-2) obtained in Production Example 2, 1.13 parts of potassium hydroxide, 1.50 parts of glycine, solid content obtained in Production Example 5 Aqueous dispersion 116.7 parts of 30% acrylic resin (e-1a), New Coal 707 (Note 3): 1 part, SN deformer 777 (Note 4): 2 parts, HEC AL-15F (Note 5): One part and water were dispersed and mixed in a container equipped with a stirrer to obtain an aqueous coating composition (S-2) having a solid content of 52%.

Example 3
100 parts of calcium hydroxide, 5.0 parts of carboxy group-containing resin (b-2) obtained in Production Example 2, 1.13 parts of potassium hydroxide, 1.50 parts of glycine, solid content obtained in Production Example 5 30% acrylic resin (e-1a) aqueous dispersion 116.7 parts, titanium white 100 parts, New Coal 707 (Note 3): 1 part, SN deformer 777 (Note 4): 2 parts, HEC AL-15F (Note 5): 1 part and water were dispersed and mixed in a container equipped with a stirrer to obtain an aqueous coating composition (S-3) having a solid content of 52%.

Example 4
73 parts of calcium hydroxide, 27 parts of calcined dolomite (calcium hydroxide: magnesium hydroxide = 63: 37 (mass ratio)), 5.0 parts of the carboxy group-containing resin (b-2) obtained in Production Example 2, water 1.13 parts of potassium oxide, 1.50 parts of glycine, 116.7 parts of an aqueous dispersion of acrylic resin (e-1a) having a solid content of 30% obtained in Production Example 5, 100 parts of titanium white, Newcor 707 ( Note 3): 1 part, SN deformer 777 (Note 4): 2 parts, HEC AL-15F (Note 5): 1 part, and water were dispersed and mixed in a vessel equipped with a stirrer to obtain a solid content of 52 % Aqueous coating composition (S-4) was obtained.

Example 5
Baked dolomite (calcium hydroxide: magnesium hydroxide = 63: 37 (mass ratio)) 100 parts, carboxy group-containing resin (b-2) obtained in Production Example 2, 5.0 parts, potassium hydroxide 1.13 parts Glycine 1.50 parts, 306.7% aqueous dispersion of acrylic resin (e-1a) obtained in Production Example 5 116.7 parts, titanium white 100 parts, New Coal 707 (Note 3): 1 part , SN deformer 777 (Note 4): 2 parts, HEC AL-15F (Note 5): 1 part, and water are dispersed and mixed in a container equipped with a stirrer to form an aqueous coating composition having a solid content of 52%. (S-5) was obtained.

Examples 6 to 32, Comparative Examples 1 to 5 (aqueous coating composition (S-6) to (S-37))
Aqueous coating compositions (S-6) to (S-37) were obtained in the same manner as the aqueous coating composition (S-3) except that the formulations shown in Tables 2 and 3 below were used. The solid content of the water-based coating composition was adjusted to 52% depending on the amount of water charged. In addition, the numerical value of the mixing | blending in Table 2 and Table 3 is solid content mass.

The notes in Table 2 and Table 3 are as follows.
(Note 1) Polyoxyethylene cetyl ether manufactured by Sanyo Chemical Co., Ltd. (Note 2) Acid-modified polyolefin resin manufactured by Unitika, weight average molecular weight 65,000, acid value 30 mgKOH / g
(Note 3) Polyoxyethylene polycyclic phenyl ether sulfate ammonium salt manufactured by Nippon Emulsifier Co., Ltd. (Note 4) Antifoaming agent manufactured by San Nopco (Note 5) Thickener manufactured by Sumitomo Seika Co., Ltd. (hydroxyethylcellulose)
(Note 6) Component (B), Component (D), Thickener and Alkali metal (C) moles per mole of acid group contained in Component (E) (Note 7) Ethylenediaminetetraacetic acid

Preparation of test coated plate "Aressic Icy Sealer" (water-based sealer manufactured by Kansai Paint Co., Ltd.) is roller-coated on a slate plate (90 x 300 x 4 mm) at about 120 g / m ² and dried at 20 ° C for 24 hours. It was. On one side, the aqueous coating compositions (S-1) to (S-37) were coated with a brush so that the dry film thickness was about 30 μm, and dried at 20 ° C. for 7 days to prepare a test coating plate. The rear surface and peripheral surface of the slate plate were coated with “Aresletan” (two-component polyurethane resin paint manufactured by Kansai Paint Co., Ltd.).

Test of coating film or paint The test of (a) to (g) was conducted on the coated surface of the coated plate. The evaluation results are shown in Table 2. Those with an evaluation of ◎ or ○ are accepted, and those with △ or × are rejected:
(A) Storage stability of paint The aqueous paint composition was stored in a sealed container at 40 ° C for 1 month, and then the paint state was evaluated.
A: No abnormality such as increase in viscosity or aggregation is observed.
○: Slight increase in viscosity is observed.
(Triangle | delta): A viscosity rises a little and the aggregate is recognized slightly.
X: Viscosity increases and aggregates are observed.

(B) Paint workability (visual evaluation of brush unevenness)
A: Brush unevenness is not recognized.
○: Brush unevenness is slightly observed.
Δ: Some brush unevenness is observed.
X: Brush unevenness is conspicuous.

(C) Finishing property: Evaluated by the number of bumps on the coating film surface of each test coating plate (evaluation of a small granular protrusion of about 1 mm or less existing on the coating film surface for one coating plate).
(Double-circle): No irregularity is recognized.
A: 1 to 5 bumps are recognized.
(Triangle | delta): 6-10 pieces are recognized.
X: 11 or more irregularities are recognized.

(D) Finishing property: Visually evaluated for streaky cracks having a length of about 1 to 2 mm on the coating film surface of each test coating board: No cracks were observed.
(Triangle | delta): A crack is recognized by 1-3 places.
X: Cracks are observed at four or more locations.

(E) In a sealable container having a deodorizing functional capacity of 20 L, put one test plate and one tissue paper soaked with 1 g of 5% aqueous acetic acid solution, and seal the lid after 24 hours at 20 ° C. Opened and examined for odor in the container.
A: Acetic acid odor is not felt.
○: A slight acetic acid odor is recognized.
Δ: A little acetic acid odor is observed.
X: Strong acetic acid odor is recognized.

(F) Adhesiveness: The surface of the coating film on the test plate was cut in a cross shape with a cutter knife, and a cellophane tape was applied to the crossing point of the scratch, and the cellophane tape was peeled off from the surface of the coating film by pulling strongly vertically. The part where the scratch on the surface of the coating film crosses was visually evaluated.
(Double-circle): Coating film peeling is not recognized.
○: Slight peeling of the coating film is observed at the cross part.
(Triangle | delta): Coating film peeling is recognized by several places around a cross | intersection part.
X: A part where the coating film is largely peeled around the cloth part is observed.

(G) Adhesiveness after immersion test: The test plate was immersed in deionized water at 20 ° C for 1 week and then dried at 20 ° C for 1 week. Thereafter, the adhesion of the coating film was evaluated by the same method as in (f).
(Double-circle): Coating film peeling is not recognized.
○: Slight coating peeling is observed at the cut part.
(Triangle | delta): Coating film peeling is recognized in several places around a cut part.
X: The place where a coating film peels largely around a cut part is recognized.

Claims (10)

Contains calcium hydroxide and / or magnesium hydroxide (A), carboxy group-containing dispersion resin (B), alkali metal compound (C), compound (D) having an amino group and an acid group, and water. An aqueous coating composition that may contain a sticky agent and / or a binder resin (E),
The alkali metal compound (C) with respect to 1 mol of the acid group contained in the carboxyl group-containing dispersion resin (B), the compound (D) having an amino group and an acid group, the thickener and the binder resin (E). Is contained in the range of 0.1 to 2.0 mol. The water-based coating composition of Claim 1 whose acid value of the said carboxyl group-containing dispersion resin (B) exists in the range of 4-400 mgKOH / g. Content of the said carboxy group containing dispersion resin (B) exists in the range of 0.5-15.0 mass parts with respect to a total of 100 mass parts of the said calcium hydroxide and / or magnesium hydroxide (A). The water-based coating composition according to claim 1 or 2. Furthermore, titanium white is included, The content is in the range of 20-150 mass parts with respect to a total of 100 mass parts of calcium hydroxide and / or magnesium hydroxide (A). The water-based coating composition according to one item. The binder resin (E) is included, and the content thereof is in the range of 10 to 100 parts by mass with respect to 100 parts by mass in total of calcium hydroxide and / or magnesium hydroxide (A). The water-based coating composition as described in any one of Claims. The content of the compound (D) having an amino group and an acid group is 0.1 to 15.0 parts by mass with respect to a total of 100 parts by mass of the calcium hydroxide and / or magnesium hydroxide (A). The aqueous coating composition according to any one of claims 1 to 5, which is within a range. The alkali metal compound (C) with respect to 1 mol of the acid group contained in the carboxyl group-containing dispersion resin (B), the compound (D) having an amino group and an acid group, the thickener and the binder resin (E). Is contained in the range of 0.2 to 1.5 mol, The water-based paint composition according to any one of claims 1 to 6, wherein The aqueous coating composition according to any one of claims 1 to 7, wherein the compound (D) having an amino group and an acid group contains a compound (D ') having an amino group and a carboxy group. The coating method of applying the water-based coating composition as described in any one of Claims 1 thru | or 8 to a to-be-coated article. A coated article obtained by applying the aqueous coating composition according to any one of claims 1 to 8 to an article to be coated.