WO2020022073A1 - Aqueous coating composition - Google Patents

Aqueous coating composition Download PDF

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Publication number
WO2020022073A1
WO2020022073A1 PCT/JP2019/027439 JP2019027439W WO2020022073A1 WO 2020022073 A1 WO2020022073 A1 WO 2020022073A1 JP 2019027439 W JP2019027439 W JP 2019027439W WO 2020022073 A1 WO2020022073 A1 WO 2020022073A1
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WO
WIPO (PCT)
Prior art keywords
resin particles
acrylic resin
meth
coating composition
solid content
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PCT/JP2019/027439
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French (fr)
Japanese (ja)
Inventor
岳 富森
勇 小金井
麗了 江森
兼基 石田
Original Assignee
関西ペイント株式会社
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Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to CN201980045138.4A priority Critical patent/CN112424298A/en
Priority to JP2020532283A priority patent/JP7381466B2/en
Publication of WO2020022073A1 publication Critical patent/WO2020022073A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to an aqueous coating composition having good film-forming properties at low temperatures and excellent corrosion protection.
  • the present invention also relates to a coated article having a cured coating film of the aqueous coating composition.
  • Emulsion paints are the mainstream in water-based paints.Emulsion paints have a much lower solvent content than solvent-based paints, but in order to improve the film-forming properties, they are water-based, but have a considerable amount as a film-forming aid. The fact is that the solvent is contained in the paint.
  • Patent Document 1 discloses an aqueous emulsion (A) of a copolymer having a minimum film-forming temperature of 0 ° C. or lower and a resin having a glass transition temperature of ⁇ 20 ° C. to 20 ° C., and a glass transition temperature of 20 ° C. or higher.
  • a resin (B) solubilized in water with an alkali, wherein the weight ratio of the nonvolatile components (A) and (B) is A / B 95/5 to 60 /
  • a resin composition for a water-based paint characterized by being in the range of 40 is disclosed.
  • the resin composition for a water-based paint is comparable to a conventional emulsion-based water-based paint containing a film-forming aid, though it contains no or very little volatile organic compound (VOC). It has a low-temperature film forming property.
  • the resin composition for a water-based paint described in Patent Document 1 has an improvement in low-temperature film-forming properties, but is insufficient in anticorrosion properties, and is desired to be improved.
  • the present invention has been made in view of the above circumstances, and has as its object to provide a water-based coating composition having good low-temperature film-forming properties and excellent anticorrosion properties.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, based on the base resin particles, an aqueous coating composition containing a specific amount of acrylic resin particles having a weight average molecular weight and an acid value in a specific range. According to this, it has been found that the above object can be achieved.
  • the present invention includes the following embodiments.
  • the resin particles (A) are different from the acrylic resin particles (B),
  • the acrylic resin particles (B) have a weight average molecular weight of 7500 to 75000 and an acid value of 10 to 90 mgKOH / g,
  • the total solid content of the resin particles (A) is 35 to 90% by weight based on the total solid content of the resin particles (A) and the acrylic resin particles (B), and the solid content of the acrylic resin particles (B) is An aqueous coating composition having a total amount of 10 to 65% by weight.
  • a coated article having a substrate and a cured coating film of the aqueous coating composition according to any one of (1) to (3) on the substrate.
  • the aqueous coating composition of the present invention having the above constitution can form a coating film having good film-forming properties at low temperatures and excellent anticorrosion properties.
  • the aqueous coating composition according to the present invention is a composition containing resin particles (A) and acrylic resin particles (B), wherein the resin particles (A) are different from the acrylic resin particles (B).
  • the acrylic resin particles (B) have a weight average molecular weight of 7500 to 75000 and an acid value of 10 to 90 mgKOH / g, and are based on the total solid content of the resin particles (A) and the acrylic resin particles (B).
  • the total solid content of the resin particles (A) is 35 to 90% by mass, and the total solid content of the acrylic resin particles (B) is 10 to 65% by mass.
  • the resin particles (A) are a base resin in an aqueous coating composition (hereinafter, may be simply referred to as “composition”).
  • the resin particles (A) include acrylic resin, acrylic / styrene resin, urethane resin, phenol resin, vinyl chloride resin, vinyl acetate resin, vinyl acetate / acrylic resin, ethylene / vinyl acetate resin, epoxy resin, and epoxy ester resin.
  • Polyester resin alkyd resin, acrylonitrile / butadiene resin, styrene / butadiene resin, polybutadiene, polyisoprene, silicone resin, fluororesin, etc., and modified products of these resins, for example, carbonate-modified urethane resin, acrylic resin-modified
  • the resin particles include at least one resin selected from epoxy resins, alkyd-modified epoxy resins, polybutadiene-modified epoxy resins, (poly) amine-modified epoxy resins, and urethane-modified epoxy resins. These resin particles may be so-called rubber.
  • the resin particles (A) are resin particles composed of a plurality of resins
  • the resin particles may be blended after the plurality of resins are blended, or may be a blend of a plurality of resin particles. These resin particles are usually blended in the composition in the form of an emulsion.
  • the resin corresponding to the acrylic resin particles (B) described later is excluded from the resin particles (A).
  • acrylic resin particles other than the acrylic resin particles (B) described below can be suitably used from the viewpoint of the corrosion resistance and weather resistance of the formed coating film.
  • epoxy resin particles can be suitably used from the viewpoint of the corrosion resistance of the formed coating film and the adhesion to the metal substrate.
  • urethane resin particles can be suitably used.
  • the minimum film forming temperature of the resin particles (A) is preferably 10 ° C or higher, more preferably 15 ° C or higher, and even more preferably 20 ° C or higher. By setting the minimum film forming temperature to 10 ° C. or higher, a decrease in hardness of the obtained coating film can be suppressed.
  • the minimum film formation temperature is a value obtained by measuring according to JIS K 6828-2 (2003). Specifically, a value measured according to JIS @ K 6828-2 (2003) in a state where ethylene glycol monobutyl ether is contained at 20% by mass with respect to the total solid content of the resin particles (A) is defined as the minimum film forming temperature.
  • the average particle diameter of the resin particles (A) is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 70 nm or more.
  • the average particle size is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the average particle diameter can be measured using a general measuring means such as laser light scattering.
  • the average particle size of the resin particles (A) in the present specification is a value measured at 20 ° C. after dilution with deionized water by a conventional method using a laser beam scattering type submicron particle size distribution analyzer. .
  • the submicron particle size distribution measuring device for example, "COULTER @ N4 type" (trade name, manufactured by Beckman Coulter, Inc.) can be used.
  • the acrylic resin particles as the resin particles (A) preferably have an anionic, nonionic or cationic hydrophilic group.
  • the presence of the hydrophilic group allows the acrylic resin particles to be well dispersed in the aqueous medium.
  • anionic hydrophilic group examples include an acidic group.
  • the acidic group examples include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These acidic groups may be neutralized by a base such as an amine.
  • nonionic hydrophilic group examples include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
  • cationic hydrophilic group examples include basic groups such as an amino group, an ammonium group, a pyridinium group, a sulfonium group, and a phosphonium group.
  • the acrylic resin particles are, for example, a polymerizable unsaturated monomer, a known method, for example, polymerized by a solution polymerization method in an organic solvent and then dispersed in water to obtain resin particles, or an emulsion polymerization method in water. Can be obtained by polymerizing according to the method described above.
  • a so-called core / shell polymerization method in which a mixture of polymerizable unsaturated monomers is fed in multiple stages, and a power feed method in which the composition of the polymerizable unsaturated monomers fed during polymerization is gradually changed can be adopted. Further, two or more kinds of acrylic resin particles produced by the above method can be used in combination.
  • Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • (meth) acrylate means acrylate or methacrylate.
  • (Meth) acrylic acid means acrylic acid or methacrylic acid.
  • (meth) acryloyl means acryloyl or methacryloyl.
  • (meth) acrylamide means acrylamide or methacrylamide.
  • acrylic resin can be used.
  • Commercial products of the acrylic resin include, for example, Polysol (registered trademark) series (manufactured by Showa Denko KK), Acryset (registered trademark) series, U-double (registered trademark) series (manufactured by Nippon Shokubai Co., Ltd.), Bon Coat Series , Watersol series (above, manufactured by DIC), Joncryl (registered trademark) series (below, manufactured by BASF), Polytron series, Polydurex series (above, made by Asahi Kasei Chemicals Corporation), Aquabrid UM-7760, 4635, same 4790 (all manufactured by Daicel Chemical Industries, Ltd.).
  • the weight average molecular weight is preferably 100,000 or more, more preferably 150,000 or more, and still more preferably 200,000 or more, from the viewpoints of corrosion resistance and hardness. Further, the weight average molecular weight is preferably 500,000 or less, more preferably 400,000 or less, and further preferably 350,000 or less.
  • the weight average molecular weight is a value obtained by converting the retention time measured using a gel permeation chromatograph into the molecular weight of polystyrene by the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. .
  • HEC-8120GPC (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and one “TSKgel @ G4000HXL” and two “TSKgel @ G3000HXL” are used as columns.
  • TSKgel @ G2000HXL (trade name, all manufactured by Tosoh Corporation) using a differential refractometer as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C.
  • the weight average molecular weight can be determined by measuring the flow rate under the condition of 1 mL / min.
  • the epoxy resin examples 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 resins obtained by modifying the above bisphenol type epoxy resin with dibasic acid; A cyclic epoxy resin; a polyglycol type epoxy resin; an epoxy group-containing acrylic resin, and the like can be used.
  • bisphenol-type epoxy resins particularly bisphenol A-type epoxy resins, can be suitably used from the viewpoints of the anti-corrosion properties of the formed coating film and the adhesion to metal substrates.
  • the epoxy resin particles as the resin particles (A) preferably have an anionic, nonionic or cationic hydrophilic group.
  • the presence of the hydrophilic group allows the epoxy resin particles to be well dispersed in the aqueous medium.
  • anionic hydrophilic group examples include an acidic group.
  • the acidic group examples include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These acidic groups may be neutralized by a base such as an amine.
  • nonionic hydrophilic group examples include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
  • the cationic hydrophilic group examples include basic groups such as an amino group, an ammonium group, a pyridinium group, a sulfonium group, and a phosphonium group.
  • the epoxy resin particles can also be obtained by adding an emulsifier to a hydrophobic epoxy resin and dispersing and emulsifying the same in water.
  • a commercial product can be used as the epoxy resin.
  • Commercial products of the epoxy resin include, for example, Watersol series (trade name, manufactured by DIC Corporation), Modepix series (trade name, manufactured by Arakawa Chemical Co., Ltd.), and ADEKARESIN (trade name, manufactured by ADEKA Corporation). it can.
  • the urethane resin particles as the resin particles (A) generally include a polyurethane comprising a polyol such as a polyester polyol or a polyether polyol and a diisocyanate, and if necessary, a polyurethane having two or more active hydrogens such as diols and diamines. It is obtained by elongating a chain in the presence of a chain extender that is a molecular weight compound and stably dispersing it in water, and known compounds can be widely used.
  • urethane resins include, for example, Hydran HW-330, HW-340, HW-350 (all manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 100, 110, 150, and F-8438D. And 420 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecabon Tyder HUX-232, 260, 320 and 350 (all manufactured by ADEKA), and the like.
  • the acrylic resin particles (B) are acrylic resin particles having a weight average molecular weight of 7,500 to 75,000 and an acid value of 10 to 90 mgKOH / g.
  • the acrylic resin particles (B) are resins that act to assist film formation in the aqueous coating composition. Specifically, in the drying process after coating, the acrylic resin particles (B) diffuse together with the phase transition and fill the voids between the resin particles (A) as the base resin. As described above, since the formation of voids in the coating film during the drying process is suppressed, the composition does not contain any film-forming aid such as a solvent at all, or even if it contains only a small amount, even at a low temperature. The film forming property can be improved.
  • the acrylic resin particles (B) can be obtained by using the same polymerization method as the acrylic resin particles described in detail in the resin particles (A) and appropriately changing the polymerization conditions.
  • the acrylic resin particles (B) are obtained by polymerizing the aforementioned polymerizable unsaturated monomer in an organic solvent by a solution polymerization method to obtain a copolymer, and then dispersing in water to obtain resin particles.
  • the manufactured product can be suitably used.
  • the weight average molecular weight of the acrylic resin particles (B) is 7500 to 75,000, preferably 9000 or more, more preferably 10,000 or more, and preferably 60,000 or less, more preferably 40,000 or less.
  • the acid value of the acrylic resin particles (B) is 10 to 90 mgKOH / g, preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g or less. It is.
  • the acid value (mgKOH / g) is represented by mg of potassium hydroxide when the amount of acid groups contained in 1 g of a sample (1 g of solid content in the case of resin) is converted into potassium hydroxide. It is.
  • the molecular weight of potassium hydroxide is 56.1.
  • Acid value (mgKOH / g) 56.1 ⁇ V ⁇ C / m V: titration (ml), C: concentration of titrant (mol / l), m: solid weight of sample (g)
  • the glass transition temperature (Tg) of the acrylic resin particles (B) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, even more preferably 20 ° C. or higher. By setting the glass transition temperature (Tg) to 0 ° C. or higher, a decrease in hardness of the obtained coating film can be prevented.
  • the glass transition temperature (Tg, ° C) of the copolymer can be calculated by the following equation.
  • n the number of types of monomers used (natural number)
  • W1 to Wn are the weight percentages of the n monomers used in the copolymerization
  • T1 to Tn are the weights of the n monomers.
  • T1 to Tn the values described in Polymer Hand Book (Second Edition, edited by J. Brandup, EH Immergut), pages III-139 to 179, can be used.
  • the glass transition temperature (° C.) when the Tg of the homopolymer of the monomer is not clear can also be obtained as a static glass transition temperature by actual measurement.
  • a sample is taken in a measuring cup, and the solvent is completely removed by vacuum suction.
  • the calorie change is measured at a temperature rate in the range of ⁇ 20 ° C. to + 200 ° C., and the first baseline change point on the low temperature side is defined as a static glass transition temperature.
  • the minimum film-forming temperature of the acrylic resin particles (B) is preferably less than 10 ° C, more preferably 7.5 ° C or less, and even more preferably 5 ° C or less. By setting the minimum film-forming temperature to less than 10 ° C., it is possible to prevent a decrease in film-forming properties and to realize good corrosion protection.
  • the SP value (solubility parameter value) of the acrylic resin particles (B) is preferably 9.3 or less, more preferably 9.0 or less. By setting the SP value to 9.3 or less, the water resistance becomes good, and the anticorrosion becomes excellent.
  • the SP value difference between the outermost layer (outermost surface layer portion) of the resin particles (A) and the acrylic resin particles (B) is preferably within 0.3, more preferably within 0.2, and preferably within 0.1. Is more preferred. When the SP value difference is within 0.3, the compatibility is good, the diffusivity is good, and the corrosion resistance is excellent.
  • solubility parameter value is as defined in Polymer ⁇ Engineering and ⁇ Science, 14, No. 2, p. 147 (1974), calculated by the following Fedors equation.
  • SP ⁇ ( ⁇ e1) / ⁇ ( ⁇ v1) ⁇ (In the formula, ⁇ e1 represents the aggregation energy per unit functional group, and ⁇ v1 represents the molecular volume per unit functional group.)
  • the SP value of a copolymer or a blend of a mixture of two or more resins is as follows: , And a value obtained by multiplying the SP value of each component of the monomer unit or the blend by the mass fraction.
  • the average particle size of the acrylic resin particles (B) is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the dispersion stability is good and the diffusivity is good, so that excellent corrosion protection is realized.
  • the total solid content of the resin particles (A) is 35 to 90% by mass based on the total solid content of the resin particles (A) and the acrylic resin particles (B), and the acrylic resin particles (B) Has a total solid content of 10 to 65% by mass.
  • the total solid content is preferably 40% by mass or more of resin particles (A) and 60% by mass or less of acrylic resin particles (B), 45% by mass or more of resin particles (A) and 55% by mass of acrylic resin particles (B). %, More preferably 80% by mass or less of the resin particles (A), 20% by mass or more of the acrylic resin particles (B), 70% by mass or less of the resin particles (A), and the acrylic resin particles (B). Is more preferably 30% by mass or more.
  • the total solid content of the resin particles (A) is 90% by mass or less, and the total solid content of the acrylic resin particles (B) is 10% by mass or more based on the total solid content of the resin particles (A) and the acrylic resin particles (B). By doing so, the film forming properties of the obtained coating film become favorable. Further, by setting the total solid content of the resin particles (A) to 35% by mass or more and the total solid content of the acrylic resin particles (B) to 65% by mass or less, the obtained coating film has good corrosion resistance. .
  • the aqueous coating composition is a mixture of the resin particles (A) and the acrylic resin particles (B), but there is no limitation in the method of mixing them. That is, both a method of adding the acrylic resin particles (B) to the resin particles (A) and a method of adding the resin particles (A) to the acrylic resin particles (B) can be adopted.
  • an acrylic resin particle (B) is used as a protective colloid and copolymerized to synthesize an aqueous emulsion, resulting in a composition in which the resin particle (A) and the acrylic resin particle (B) coexist. You can also.
  • the aqueous paint composition preferably has a pH of 5.0 or more, more preferably 6.0 or more, and preferably 10.0 or less, more preferably 9.0 or less.
  • the aqueous coating composition may contain a crosslinking agent, a curing catalyst, a pigment such as a coloring pigment, a filler, an aggregate, a dispersant, a wetting agent, a thickener, a rheology control agent, a surface conditioning agent, Foaming agents, preservatives, fungicides, pH adjusters, rust inhibitors, anti-settling agents, anti-freezing agents, anti-skinning agents, ultraviolet absorbers, antioxidants, organic solvents and the like can also be included.
  • the water-based coating composition is a cured coating film which is applied and cured on various substrates, preferably a metal substrate, as required.
  • the coating can be applied once or twice or more by a conventionally known method such as roller coating, spray coating, brush coating, curtain coating, shower coating, dip coating, etc. to form a coating film.
  • the base material is a metal base material
  • the water-based coating composition according to the present embodiment is applied on the metal base material, and cured to form a cured coating film.
  • a coated article having excellent anticorrosion properties can be obtained.
  • the coating film of the aqueous coating composition is preferably cured at room temperature from the viewpoint of energy saving and the like.
  • the thickness of the cured coating film obtained by applying the aqueous coating composition is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, from the viewpoints of corrosion resistance, water resistance, hardness, and the like of the formed cured coating film. 25 ⁇ m or more is further preferable, 200 ⁇ m or less is preferable, 100 ⁇ m or less is more preferable, and 60 ⁇ m or less is further preferable.
  • the component (A2) and the component (B1) ) Component and (B2) component), and an aqueous solution of initiator 1 (in Table 1, VA-057 is a trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 2-2'-azobis [N- (2-carboxyethyl) -2-methylpropiondiamine] tetrahydrate) was added dropwise over 3 hours to polymerize. After the completion of the dropwise addition, the reaction was carried out at 82 ° C. for 0.5 hour, and the initiator 2 aqueous solution was added dropwise over 0.5 hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C for 1.5 hours, and then cooled to 25 ° C.
  • VA-057 is a trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 2-2'-azobis [N- (2-carboxyethyl) -2-methylpropiondiamine] tetrahydrate
  • the emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 420 mPa ⁇ s, a pH of 9.2 (measured with a pH meter), and an average particle diameter of 130 nm.
  • the dropping of the (A1) component emulsion was completed, the dropping of the (B2) component emulsion shown in Table 1 was started, and was dropped at about 146.0 parts / hour.
  • the reaction was carried out at 82 ° C. for 0.5 hour, and an aqueous solution of initiator 2 was added dropwise at about 3.3 parts / hour.
  • the reaction was carried out at 82 ° C for 1.5 hours, and then cooled to 25 ° C.
  • the emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 400 mPa ⁇ s, a pH of 9.2 (measured with a pH meter), and an average particle size of 120 nm.
  • the dropping of the (A1) component emulsion was completed, the dropping of the (A2) component emulsion shown in Table 1 was started.
  • the component (B1) emulsion shown in Table 1 was dropped into the component (A2) emulsion.
  • the dropping rate of the component (B1) emulsion was set to a rate at which the dropping was completed simultaneously with the dropping of the component (A2) emulsion, that is, about 73.0 parts / hour in the present production example.
  • the component (B2) emulsion was dropped at about 146.0 parts / hour.
  • the reaction was carried out at 82 ° C.
  • the emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 710 mPa ⁇ s, a pH of 9.2 (measured with a pH meter), and an average particle diameter of 100 nm.
  • the minimum film forming temperature of the resin particles (A-1) to (A-3) is a value measured by adding 20% by mass of ethylene glycol monobutyl ether to the total solid content of each resin particle. .
  • Production Example 4 A reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping device was charged with 20 parts of ethylene glycol monobutyl ether and 14 parts of propylene glycol monomethyl ether, and heated to 115 ° C., and then 10 parts of styrene.
  • the obtained acrylic copolymer 1 had an SP value of 9.12, an acid value of 66 mgKOH / g, and a weight average molecular weight of about 2,200.
  • the obtained resin particles (A-4) had an average particle diameter of 200 nm and an acid value of 44 mgKOH / g.
  • the obtained acrylic resin particles (B-1) have a weight average molecular weight of 9000, an acid value of 45.4 mg KOH / g, a glass transition temperature of 41.7 ° C., an SP value of 8.98, an average particle diameter of 180 nm, and a minimum of The film formation temperature was 0 ° C.
  • Acrylic resin particles (B-2) to (B-11) were obtained in the same manner as in Production Example 5, except that the composition was changed to that shown in Table 2. All initiators used perbutyl O as in Production Example 5 (allocation ratio was the same as in Production Example 5). Table 2 also shows the weight average molecular weight, acid value, glass transition temperature, SP value, average particle diameter, and minimum film forming temperature (° C.) of each of the obtained acrylic resin particles.
  • the acrylic resin particles (B-8) to (B-11) are used as comparative examples.
  • Example 1 DISPERBYK (registered trademark) -190 (trade name, manufactured by BYK, pigment dispersant, solid content: 40%) 3 parts (solid content: 1.2 parts), BYK (registered trademark) -024 (trade name, manufactured by BYK, 0.4 parts of antifoaming agent, solid content 100%), 35 parts of JR-603 (trade name, manufactured by Teika, titanium oxide, solid content 100%), Super SS (trade name, manufactured by Maruo Calcium Co., calcium carbonate, 15 parts of solid content 100%), 25 parts of deionized water and 2 parts of dipropylene glycol monomethyl ether were mixed, and after adding glass beads, the mixture was dispersed with a paint shaker for 60 minutes to obtain a pigment paste (P1) (solid content of 64.2%). ) Got.
  • P1 solid content of 64.2%
  • Corrosion resistance With respect to each test plate, the coating film was cut with a knife to reach the base material with a knife, and 120 hours in accordance with JIS K 5600-7-1 (1999) "Neutral salt spray resistance" A salt spray test was performed. Evaluation was made according to the following criteria based on the width of rust and blisters from knife scratches. The smaller the maximum width of rust and blisters, the better the anticorrosion. If the rating is A to C, the anticorrosion is good.
  • the specular gloss (60 °) of the coated surface was measured in accordance with JIS K 5600-4-7 (1999) “Specular gloss”. If the specular gloss (60 °) of the coated surface is 70 or more, the gloss is good.
  • Pencil hardness The pencil hardness of the coated surface of each test plate was measured in accordance with JIS K 5600-5-4 (1999) “Scratch hardness (pencil method)”. Pencil hardness is F, HB, B, 2B in order from the harder one. If the hardness is B or more, the hardness is good.

Abstract

The purpose of the present invention is to provide an aqueous coating composition which exhibits good film forming properties at low temperatures, while having excellent anti-corrosion properties. The present invention is an aqueous coating composition which contains resin particles (A) and acrylic resin particles (B), and which is configured such that: the resin particles (A) are different from the acrylic resin particles (B); the acrylic resin particles (B) have a weight average molecular weight of from 7,500 to 75,000 and an acid value of from 10 mgKOH/g to 90 mgKOH/g; and the ratio of the total amount of solid contents in the resin particles (A) to the total amount of solid contents in the acrylic resin particles (B) is from 35:65 to 90:10.

Description

水性塗料組成物Aqueous paint composition
　本発明は、低温での造膜性が良好で、防食性にも優れる水性塗料組成物に関する。また、前記水性塗料組成物の硬化塗膜を有する塗装物品にも関する。 The present invention relates to an aqueous coating composition having good film-forming properties at low temperatures and excellent corrosion protection. The present invention also relates to a coated article having a cured coating film of the aqueous coating composition.
　近年、地球環境保護及び安全衛生上の観点から、溶剤系塗料から水系塗料への転換が進められており、金属基材等の防食塗料分野においても水性防食塗料の開発が行われている。 In recent years, from the viewpoints of global environmental protection and health and safety, conversion from solvent-based paints to water-based paints has been promoted, and water-based anticorrosive paints have been developed in the field of anticorrosive paints such as metal substrates.
　水性塗料においてはエマルション塗料が主流であり、エマルション塗料は溶剤系塗料と比べると溶剤の含有量は格段に少ないが、造膜性向上のために、水性といえども造膜助剤として、相当量の溶剤を塗料中に含んでいるのが実情である。 Emulsion paints are the mainstream in water-based paints.Emulsion paints have a much lower solvent content than solvent-based paints, but in order to improve the film-forming properties, they are water-based, but have a considerable amount as a film-forming aid. The fact is that the solvent is contained in the paint.
　造膜助剤添加以外の造膜性を向上する手法として、エマルション樹脂を軟質化する方法があるが、得られる塗膜の硬度が低下して、防食性等の塗膜性能も低下する。 手法 As a method of improving the film-forming properties other than the addition of a film-forming aid, there is a method of softening an emulsion resin. However, the hardness of the obtained coating film is reduced, and the coating film performance such as anti-corrosion property is also reduced.
　特許文献１には、最低造膜温度が０℃以下であり、かつ樹脂のガラス転移温度が－２０℃から２０℃である共重合体の水性エマルジョン（Ａ）と、ガラス転移温度が２０℃以上のアルカリにより水に可溶化された樹脂（Ｂ）とからなる組成物であって、上記（Ａ）と上記（Ｂ）との不揮発分の重量比が、Ａ／Ｂ＝９５／５～６０／４０の範囲にあることを特徴とする水性塗料用樹脂組成物が開示されている。該水性塗料用樹脂組成物によれば、揮発性有機化合物（ＶＯＣ）を全く含まないか、含んでもごく微量であるにもかかわらず、従来の造膜助剤の入ったエマルジョンベースの水性塗料並みの低温成膜性を有することが記載されている。 Patent Document 1 discloses an aqueous emulsion (A) of a copolymer having a minimum film-forming temperature of 0 ° C. or lower and a resin having a glass transition temperature of −20 ° C. to 20 ° C., and a glass transition temperature of 20 ° C. or higher. A resin (B) solubilized in water with an alkali, wherein the weight ratio of the nonvolatile components (A) and (B) is A / B = 95/5 to 60 / A resin composition for a water-based paint characterized by being in the range of 40 is disclosed. According to the resin composition for a water-based paint, it is comparable to a conventional emulsion-based water-based paint containing a film-forming aid, though it contains no or very little volatile organic compound (VOC). It has a low-temperature film forming property.
日本国特開平１１－３４３４６４号公報Japanese Patent Application Laid-Open No. 11-343664
　しかしながら、特許文献１に記載の水性塗料用樹脂組成物は、低温成膜性の向上は認められるものの、防食性が不十分であり、改善が望まれる。 However, the resin composition for a water-based paint described in Patent Document 1 has an improvement in low-temperature film-forming properties, but is insufficient in anticorrosion properties, and is desired to be improved.
　本発明は上記事情を勘案してなされたものであり、低温での造膜性が良好で、かつ防食性にも優れる水性塗料組成物を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and has as its object to provide a water-based coating composition having good low-temperature film-forming properties and excellent anticorrosion properties.
　本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、基体樹脂粒子に対し、特定範囲の重量平均分子量及び酸価を有するアクリル樹脂粒子を特定量含有する水性塗料組成物によれば、上記目的を達成できることを見出した。 The present inventors have conducted intensive studies to achieve the above object, and as a result, based on the base resin particles, an aqueous coating composition containing a specific amount of acrylic resin particles having a weight average molecular weight and an acid value in a specific range. According to this, it has been found that the above object can be achieved.
　即ち、本発明は、下記の態様を包含する。 That is, the present invention includes the following embodiments.
（１）樹脂粒子（Ａ）及びアクリル樹脂粒子（Ｂ）を含有する組成物であって、
　前記樹脂粒子（Ａ）は前記アクリル樹脂粒子（Ｂ）とは異なり、
　前記アクリル樹脂粒子（Ｂ）は重量平均分子量が７５００～７５０００、かつ酸価が１０～９０ｍｇＫＯＨ／ｇであり、
　前記樹脂粒子（Ａ）及び前記アクリル樹脂粒子（Ｂ）の固形分総量に対して、前記樹脂粒子（Ａ）の固形分総量が３５～９０重量％、かつ前記アクリル樹脂粒子（Ｂ）の固形分総量が１０～６５重量％である水性塗料組成物。 (1) A composition containing resin particles (A) and acrylic resin particles (B),
The resin particles (A) are different from the acrylic resin particles (B),
The acrylic resin particles (B) have a weight average molecular weight of 7500 to 75000 and an acid value of 10 to 90 mgKOH / g,
The total solid content of the resin particles (A) is 35 to 90% by weight based on the total solid content of the resin particles (A) and the acrylic resin particles (B), and the solid content of the acrylic resin particles (B) is An aqueous coating composition having a total amount of 10 to 65% by weight.
（２）前記アクリル樹脂粒子（Ｂ）のガラス転移温度が０℃以上である前記（１）に記載の水性塗料組成物。 (2) The aqueous coating composition according to (1), wherein the acrylic resin particles (B) have a glass transition temperature of 0 ° C. or higher.
（３）前記樹脂粒子（Ａ）の最外層と前記アクリル樹脂粒子（Ｂ）のＳＰ値差が０．３以内である前記（１）又は（２）に記載の水性塗料組成物。 (3) The aqueous coating composition according to (1) or (2), wherein the SP value difference between the outermost layer of the resin particles (A) and the acrylic resin particles (B) is within 0.3.
（４）基材と、前記基材上に前記（１）～（３）のいずれか一に記載の水性塗料組成物の硬化塗膜とを有する塗装物品。 (4) A coated article having a substrate and a cured coating film of the aqueous coating composition according to any one of (1) to (3) on the substrate.
（５）前記基材が金属基材である前記（４）に記載の塗装物品。 (5) The coated article according to (4), wherein the substrate is a metal substrate.
　本発明の水性塗料組成物は、上記構成を有することにより、低温での造膜性が良好であり、かつ防食性にも優れる塗膜を形成することができる。 水性 The aqueous coating composition of the present invention having the above constitution can form a coating film having good film-forming properties at low temperatures and excellent anticorrosion properties.
　以下、本発明の水性塗料組成物について、さらに詳細に説明する。なお、本明細書において、‘質量％’と‘重量％’、‘質量部’と‘重量部’とは、それぞれ同義である。 Hereinafter, the aqueous coating composition of the present invention will be described in more detail. In this specification, the terms "% by mass" and "% by weight" and "parts by mass" and "parts by weight" have the same meanings.
　本発明に係る水性塗料組成物は、樹脂粒子（Ａ）及びアクリル樹脂粒子（Ｂ）を含有する組成物であって、前記樹脂粒子（Ａ）は前記アクリル樹脂粒子（Ｂ）とは異なり、前記アクリル樹脂粒子（Ｂ）は重量平均分子量が７５００～７５０００、かつ酸価が１０～９０ｍｇＫＯＨ／ｇであり、前記樹脂粒子（Ａ）及び前記アクリル樹脂粒子（Ｂ）の固形分総量に対して、前記樹脂粒子（Ａ）の固形分総量が３５～９０質量％、かつ前記アクリル樹脂粒子（Ｂ）の固形分総量が１０～６５質量％であることを特徴とするものである。 The aqueous coating composition according to the present invention is a composition containing resin particles (A) and acrylic resin particles (B), wherein the resin particles (A) are different from the acrylic resin particles (B). The acrylic resin particles (B) have a weight average molecular weight of 7500 to 75000 and an acid value of 10 to 90 mgKOH / g, and are based on the total solid content of the resin particles (A) and the acrylic resin particles (B). The total solid content of the resin particles (A) is 35 to 90% by mass, and the total solid content of the acrylic resin particles (B) is 10 to 65% by mass.
＜樹脂粒子（Ａ）＞
　樹脂粒子（Ａ）は水性塗料組成物（以下、単に「組成物」と称することがある。）における基体樹脂である。樹脂粒子（Ａ）としては、例えば、アクリル樹脂、アクリル／スチレン樹脂、ウレタン樹脂、フェノール樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、酢酸ビニル／アクリル樹脂、エチレン／酢酸ビニル樹脂、エポキシ樹脂、エポキシエステル樹脂、ポリエステル樹脂、アルキド樹脂、アクリロニトリル／ブタジエン樹脂、スチレン／ブタジエン樹脂、ポリブタジエン、ポリイソプレン、シリコン樹脂、及びフッ素樹脂等、並びに、これらの樹脂を変性したもの、例えば、カーボネート変性ウレタン樹脂、アクリル樹脂変性エポキシ樹脂、アルキド変性エポキシ樹脂、ポリブタジエン変性エポキシ樹脂、（ポリ）アミン変性エポキシ樹脂、ウレタン変性エポキシ樹脂等の樹脂から選ばれる少なくとも１種からなる樹脂粒子を挙げることができる。これらの樹脂粒子はいわゆるゴムであってもよい。 <Resin particles (A)>
The resin particles (A) are a base resin in an aqueous coating composition (hereinafter, may be simply referred to as “composition”). Examples of the resin particles (A) include acrylic resin, acrylic / styrene resin, urethane resin, phenol resin, vinyl chloride resin, vinyl acetate resin, vinyl acetate / acrylic resin, ethylene / vinyl acetate resin, epoxy resin, and epoxy ester resin. , Polyester resin, alkyd resin, acrylonitrile / butadiene resin, styrene / butadiene resin, polybutadiene, polyisoprene, silicone resin, fluororesin, etc., and modified products of these resins, for example, carbonate-modified urethane resin, acrylic resin-modified Examples of the resin particles include at least one resin selected from epoxy resins, alkyd-modified epoxy resins, polybutadiene-modified epoxy resins, (poly) amine-modified epoxy resins, and urethane-modified epoxy resins. These resin particles may be so-called rubber.
　樹脂粒子（Ａ）が複数の樹脂からなる樹脂粒子である場合には、複数の樹脂をブレンドした後に樹脂粒子としてもよく、複数の樹脂粒子のブレンドであってもよい。これらの樹脂粒子は、通常、エマルションの形態で組成物中に配合される。 In the case where the resin particles (A) are resin particles composed of a plurality of resins, the resin particles may be blended after the plurality of resins are blended, or may be a blend of a plurality of resin particles. These resin particles are usually blended in the composition in the form of an emulsion.
　なお、本実施形態において、後記アクリル樹脂粒子（Ｂ）に該当する樹脂は、樹脂粒子（Ａ）からは除外されるものとする。 In this embodiment, the resin corresponding to the acrylic resin particles (B) described later is excluded from the resin particles (A).
　これらの樹脂粒子（Ａ）のうち、形成される塗膜の防食性及び耐候性の観点から、後記アクリル樹脂粒子（Ｂ）以外のアクリル樹脂粒子を好適に使用することができる。また、形成される塗膜の防食性及び金属基材への付着性の観点から、エポキシ樹脂粒子を好適に使用することができる。塗膜の強靱性の観点からは、ウレタン樹脂粒子を好適に使用することができる。 ア ク リ ル Among these resin particles (A), acrylic resin particles other than the acrylic resin particles (B) described below can be suitably used from the viewpoint of the corrosion resistance and weather resistance of the formed coating film. In addition, epoxy resin particles can be suitably used from the viewpoint of the corrosion resistance of the formed coating film and the adhesion to the metal substrate. From the viewpoint of the toughness of the coating film, urethane resin particles can be suitably used.
　樹脂粒子（Ａ）の最低造膜温度は１０℃以上が好ましく、１５℃以上がより好ましく、２０℃以上がさらに好ましい。最低造膜温度を１０℃以上とすることにより、得られる塗膜の硬度低下を抑制することができる。 最低 The minimum film forming temperature of the resin particles (A) is preferably 10 ° C or higher, more preferably 15 ° C or higher, and even more preferably 20 ° C or higher. By setting the minimum film forming temperature to 10 ° C. or higher, a decrease in hardness of the obtained coating film can be suppressed.
　本明細書において、最低造膜温度はＪＩＳ　Ｋ　６８２８－２（２００３）に従って測定することにより得られる値である。具体的には、樹脂粒子（Ａ）の固形分総量に対してエチレングリコールモノブチルエーテルを２０質量％含有する状態でＪＩＳ　Ｋ　６８２８－２（２００３）に従って測定した値を最低造膜温度と定義する。 に お い て In the present specification, the minimum film formation temperature is a value obtained by measuring according to JIS K 6828-2 (2003). Specifically, a value measured according to JIS @ K 6828-2 (2003) in a state where ethylene glycol monobutyl ether is contained at 20% by mass with respect to the total solid content of the resin particles (A) is defined as the minimum film forming temperature.
　樹脂粒子（Ａ）の平均粒子径は、５０ｎｍ以上が好ましく、６０ｎｍ以上がより好ましく、７０ｎｍ以上がさらに好ましい。また平均粒子径は、５００ｎｍ以下が好ましく、４００ｎｍ以下がより好ましく、３００ｎｍ以下がさらに好ましい。 The average particle diameter of the resin particles (A) is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 70 nm or more. The average particle size is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
　平均粒子径を５０ｎｍ以上とすることにより、粘度が高くなり過ぎるのを防ぐことができ、良好なハンドリングを維持することができる。また、平均粒子径を５００ｎｍ以下とすることにより、分散安定性が良好となる。 こ と By setting the average particle diameter to 50 nm or more, it is possible to prevent the viscosity from becoming too high, and to maintain good handling. Further, by setting the average particle size to 500 nm or less, the dispersion stability is improved.
　平均粒子径はレーザー光散乱等の一般的な測定手段を用いて測定することができる。 The average particle diameter can be measured using a general measuring means such as laser light scattering.
　本明細書における樹脂粒子（Ａ）の平均粒子径は、レーザー光散乱式であるサブミクロン粒度分布測定装置を用いて、常法により脱イオン水で希釈してから２０℃で測定した値である。サブミクロン粒度分布測定装置としては、例えば、「ＣＯＵＬＴＥＲ　Ｎ４型」（商品名、ベックマン・コールター社製）を使用することができる。 The average particle size of the resin particles (A) in the present specification is a value measured at 20 ° C. after dilution with deionized water by a conventional method using a laser beam scattering type submicron particle size distribution analyzer. . As the submicron particle size distribution measuring device, for example, "COULTER @ N4 type" (trade name, manufactured by Beckman Coulter, Inc.) can be used.
　樹脂粒子（Ａ）としての上記アクリル樹脂粒子は、アニオン性、ノニオン性又はカチオン性の親水性基を有していることが好ましい。親水性基が存在することにより、アクリル樹脂粒子は水系媒体へ良好に分散することができる。 ア ク リ ル The acrylic resin particles as the resin particles (A) preferably have an anionic, nonionic or cationic hydrophilic group. The presence of the hydrophilic group allows the acrylic resin particles to be well dispersed in the aqueous medium.
　前記アニオン性の親水性基としては、例えば酸性基を挙げることができる。該酸性基としては、例えばカルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等を挙げることができる。これらの酸性基はアミン等の塩基によって中和されていてもよい。 と し て Examples of the anionic hydrophilic group include an acidic group. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These acidic groups may be neutralized by a base such as an amine.
　前記ノニオン性の親水性基としては、例えばポリエチレングリコール基、ポリグリセリン基、親水性糖鎖基等を挙げることができる。 と し て Examples of the nonionic hydrophilic group include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
　前記カチオン性の親水性基としては、例えばアミノ基、アンモニウム基、ピリジニウム基、スルホニウム基、ホスホニウム基等の塩基性基を挙げることができる。 {Examples of the cationic hydrophilic group include basic groups such as an amino group, an ammonium group, a pyridinium group, a sulfonium group, and a phosphonium group.
　上記アクリル樹脂粒子は、例えば、重合性不飽和モノマーを、既知の方法、例えば、有機溶媒中で溶液重合法で重合した後に水分散して樹脂粒子とする方法や、水中でのエマルション重合法等の方法により重合せしめることによって得ることができる。 The acrylic resin particles are, for example, a polymerizable unsaturated monomer, a known method, for example, polymerized by a solution polymerization method in an organic solvent and then dispersed in water to obtain resin particles, or an emulsion polymerization method in water. Can be obtained by polymerizing according to the method described above.
　また、重合性不飽和モノマーの混合物を多段でフィードするいわゆるコア／シェル重合法や、重合中にフィードする重合性不飽和モノマーの組成を逐次変化させるパワーフィード法を採用することもできる。更に上記方法で製造した２種以上のアクリル樹脂粒子を混合して使用することもできる。 い わ ゆ る Also, a so-called core / shell polymerization method in which a mixture of polymerizable unsaturated monomers is fed in multiple stages, and a power feed method in which the composition of the polymerizable unsaturated monomers fed during polymerization is gradually changed can be adopted. Further, two or more kinds of acrylic resin particles produced by the above method can be used in combination.
　これらの方法のうち、エマルション重合により得られたものを好適に使用することができる。 の う ち Among these methods, those obtained by emulsion polymerization can be suitably used.
　上記重合性不飽和モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、「イソステアリルアクリレート」（商品名、大阪有機化学工業社製）、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等のイソボルニル基を有する重合性不飽和モノマー；アダマンチル（メタ）アクリレート等のアダマンチル基を有する重合性不飽和モノマー；スチレン、α－メチルスチレン、ビニルトルエン等のビニル芳香族化合物；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリエトキシシラン等のアルコキシシリル基を有する重合性不飽和モノマー；パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等のフッ素化アルキル基を有する重合性不飽和モノマー；マレイミド基等の光重合性官能基を有する重合性不飽和モノマー；Ｎ－ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等のビニル化合物；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物、該（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物のε－カプロラクトン変性体、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、アリルアルコール、分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等の水酸基含有重合性不飽和モノマー；（メタ）アクリル酸、マレイン酸、クロトン酸、β－カルボキシエチル（メタ）アクリレート等のカルボキシル基含有重合性不飽和モノマー；（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、グリシジル（メタ）アクリレートとアミン化合物との付加物等の含窒素重合性不飽和モノマー；アリル（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート等の重合性不飽和基を１分子中に２個以上有する重合性不飽和モノマー；グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３，４－エポキシシクロヘキシルエチル（メタ）アクリレート、３，４－エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有重合性不飽和モノマー；分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート；２－アクリルアミド－２－メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレート及びそのナトリウム塩、アンモニウム塩等のスルホン酸基を有する重合性不飽和モノマー；２－アクリロイルオキシエチルアシッドホスフェート、２－メタクリロイルオキシエチルアシッドホスフェート、２－アクリロイルオキシプロピルアシッドホスフェート、２－メタクリロイルオキシプロピルアシッドホスフェート等のリン酸基を有する重合性不飽和モノマー；２－ヒドロキシ－４－（３－メタクリロイルオキシ－２－ヒドロキシプロポキシ）ベンゾフェノン、２－ヒドロキシ－４－（３－アクリロイルオキシ－２－ヒドロキシプロポキシ）ベンゾフェノン、２，２’－ジヒドロキシ－４－（３－メタクリロイルオキシ－２－ヒドロキシプロポキシ）ベンゾフェノン、２，２’－ジヒドロキシ－４－（３－アクリロイルオキシ－２－ヒドロキシプロポキシ）ベンゾフェノン、２－（２’－ヒドロキシ－５’－メタクリロイルオキシエチルフェニル）－２Ｈ－ベンゾトリアゾール等の紫外線吸収性官能基を有する重合性不飽和モノマー；４－（メタ）アクリロイルオキシ－１，２，２，６，６－ペンタメチルピペリジン、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－シアノ－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、１－（メタ）アクリロイル－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、１－（メタ）アクリロイル－４－シアノ－４－（メタ）アクリロイルアミノ－２，２，６，６－テトラメチルピペリジン、４－クロトノイルオキシ－２，２，６，６－テトラメチルピペリジン、４－クロトノイルアミノ－２，２，６，６－テトラメチルピペリジン、１－クロトノイル－４－クロトノイルオキシ－２，２，６，６－テトラメチルピペリジン等の紫外線安定性重合性不飽和モノマー；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４～７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基を有する重合性不飽和モノマー化合物等を挙げることができ、これらはそれぞれ単独でもしくは２種以上を組合せて使用することができる。 Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, "isostearyl acrylate" (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl Alkyl or cycloalkyl (meth) acrylate such as meth) acrylate and cyclododecyl (meth) acrylate; polymerizable unsaturated monomer having an isobornyl group such as isobornyl (meth) acrylate; polymerization having an adamantyl group such as adamantyl (meth) acrylate Unsaturated monomers; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxy Polymerizable unsaturated monomers having an alkoxysilyl group such as silane and γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethyl Perfluoroalkyl (meth) acrylates such as (meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; polymerizable unsaturated monomers having a photopolymerizable functional group such as a maleimide group; N-vinyl Vinyl compounds such as pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, and vinyl acetate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl Monoester of (meth) acrylic acid such as (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms, and ε of monoester of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms -Modified caprolactone, N-hydroxymethyl ( (T) hydroxyl-containing polymerizable unsaturated monomers such as acrylamide, allyl alcohol, and (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end; (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl ( Carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylate; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, glycidyl ( Nitrogen-containing polymerizable unsaturated monomers such as adducts of (meth) acrylates and amine compounds; polymerizable unsaturated groups such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate in one molecule. Glycidyl (meth) (T) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl Epoxy group-containing polymerizable unsaturated monomers such as glycidyl ether; (meth) acrylate having a polyoxyethylene chain having an alkoxy group at the molecular end; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonate Polymerizable unsaturated monomers having a sulfonic acid group such as salts, sulfoethyl methacrylates and their sodium salts and ammonium salts; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl Polymerizable unsaturated monomers having a phosphate group, such as acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate; 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone; 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- Polymerizable having an ultraviolet absorbing functional group such as (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole Unsaturated monomer; 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano- 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- ( (Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyl Amino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine UV-stable polymerizable unsaturated monomers; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone) , Vinyl butyl ketone) and other polymerizable unsaturated monomer compounds having a carbonyl group. These can be used alone or in combination of two or more.
　本明細書において、「（メタ）アクリレート」はアクリレート又はメタクリレートを意味する。「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。また、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。また、「（メタ）アクリルアミド」は、アクリルアミド又はメタクリルアミドを意味する。 に お い て In the present specification, “(meth) acrylate” means acrylate or methacrylate. "(Meth) acrylic acid" means acrylic acid or methacrylic acid. Further, “(meth) acryloyl” means acryloyl or methacryloyl. Further, “(meth) acrylamide” means acrylamide or methacrylamide.
　上記アクリル樹脂としては市販品を使用することができる。該アクリル樹脂の市販品としては、例えば、ポリゾール（登録商標）シリーズ（昭和電工社製）、アクリセット（登録商標）シリーズ、ユーダブル（登録商標）シリーズ（以上、日本触媒社製）、ボンコートシリーズ、ウォーターゾールシリーズ（以上、ＤＩＣ社製）、ジョンクリル（登録商標）シリーズ（ＢＡＳＦ社製）、ポリトロンシリーズ、ポリデュレックスシリーズ（以上、旭化成ケミカルズ社製）、アクアブリッドＵＭ－７７６０、同４６３５、同４７９０（いずれもダイセル化学工業社製）等を挙げることができる。 市 販 A commercially available acrylic resin can be used. Commercial products of the acrylic resin include, for example, Polysol (registered trademark) series (manufactured by Showa Denko KK), Acryset (registered trademark) series, U-double (registered trademark) series (manufactured by Nippon Shokubai Co., Ltd.), Bon Coat Series , Watersol series (above, manufactured by DIC), Joncryl (registered trademark) series (below, manufactured by BASF), Polytron series, Polydurex series (above, made by Asahi Kasei Chemicals Corporation), Aquabrid UM-7760, 4635, same 4790 (all manufactured by Daicel Chemical Industries, Ltd.).
　樹脂粒子（Ａ）が、アクリル樹脂粒子である場合、防食性や硬度の観点から、重量平均分子量は１０万以上が好ましく、１５万以上がより好ましく、２０万以上がさらに好ましい。また、重量平均分子量は５０万以下が好ましく、４０万以下がより好ましく、３５万以下がさらに好ましい。 (4) When the resin particles (A) are acrylic resin particles, the weight average molecular weight is preferably 100,000 or more, more preferably 150,000 or more, and still more preferably 200,000 or more, from the viewpoints of corrosion resistance and hardness. Further, the weight average molecular weight is preferably 500,000 or less, more preferably 400,000 or less, and further preferably 350,000 or less.
　重量平均分子量が１０万以上であると、防食性や硬度が良好となり、また５０万以下であると、良好な成膜性が得られ防食性も良好になる。 (4) When the weight average molecular weight is 100,000 or more, good anticorrosion properties and hardness are obtained, and when the weight average molecular weight is 500,000 or less, good film-forming properties and good anticorrosion properties are obtained.
　本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフを用いて測定した保持時間を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間によりポリスチレンの分子量に換算して求めた値である。 In the present specification, the weight average molecular weight is a value obtained by converting the retention time measured using a gel permeation chromatograph into the molecular weight of polystyrene by the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. .
　具体的には、例えば、ゲルパーミエーションクロマトグラフ装置として、「ＨＬＣ－８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ　Ｇ４０００ＨＸＬ」を１本、「ＴＳＫｇｅｌ　Ｇ３０００ＨＸＬ」を２本、及び「ＴＳＫｇｅｌ　Ｇ２０００ＨＸＬ」を１本（商品名、いずれも東ソー社製）の計４本を使用し、検出器として、示差屈折率計を使用し、移動相：テトラヒドロフラン、測定温度：４０℃、流速：１ｍＬ／ｍｉｎの条件下で測定することで、重量平均分子量を求めることができる。 Specifically, for example, “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and one “TSKgel @ G4000HXL” and two “TSKgel @ G3000HXL” are used as columns. , And one TSKgel @ G2000HXL (trade name, all manufactured by Tosoh Corporation) using a differential refractometer as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., The weight average molecular weight can be determined by measuring the flow rate under the condition of 1 mL / min.
　前記エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；上記ビスフェノール型エポキシ樹脂を二塩基酸等で変性したエポキシエステル樹脂；脂環式エポキシ樹脂；ポリグリコール型エポキシ樹脂；エポキシ基含有アクリル樹脂等を使用することができる。これらのうち、形成される塗膜の防食性、金属基材への付着性等の観点から、ビスフェノール型エポキシ樹脂、特にビスフェノールＡ型エポキシ樹脂を好適に使用することができる。 Examples of the epoxy resin 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 resins obtained by modifying the above bisphenol type epoxy resin with dibasic acid; A cyclic epoxy resin; a polyglycol type epoxy resin; an epoxy group-containing acrylic resin, and the like can be used. Of these, bisphenol-type epoxy resins, particularly bisphenol A-type epoxy resins, can be suitably used from the viewpoints of the anti-corrosion properties of the formed coating film and the adhesion to metal substrates.
　樹脂粒子（Ａ）としての上記エポキシ樹脂粒子は、アニオン性、ノニオン性又はカチオン性の親水性基を有していることが好ましい。親水性基が存在することにより、エポキシ樹脂粒子として水系媒体へ良好に分散することができる。 The epoxy resin particles as the resin particles (A) preferably have an anionic, nonionic or cationic hydrophilic group. The presence of the hydrophilic group allows the epoxy resin particles to be well dispersed in the aqueous medium.
　前記アニオン性の親水性基としては、例えば酸性基が挙げられる。該酸性基としては、例えばカルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等を挙げることができる。これらの酸性基はアミン等の塩基によって中和されていてもよい。 と し て Examples of the anionic hydrophilic group include an acidic group. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These acidic groups may be neutralized by a base such as an amine.
　前記ノニオン性の親水性基としては、例えばポリエチレングリコール基、ポリグリセリン基、親水性糖鎖基等を挙げることができる。 と し て Examples of the nonionic hydrophilic group include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
　前記カチオン性の親水性基としては、例えばアミノ基、アンモニウム基、ピリジニウム基、スルホニウム基、ホスホニウム基等の塩基性基を挙げることができる。
　また、エポキシ樹脂粒子は、疎水性のエポキシ樹脂に乳化剤を加えて水中で分散乳化することにより得ることもできる。 Examples of the cationic hydrophilic group include basic groups such as an amino group, an ammonium group, a pyridinium group, a sulfonium group, and a phosphonium group.
The epoxy resin particles can also be obtained by adding an emulsifier to a hydrophobic epoxy resin and dispersing and emulsifying the same in water.
　上記エポキシ樹脂としては市販品を使用することができる。該エポキシ樹脂の市販品としては、例えば、ウォーターゾールシリーズ（商品名、ＤＩＣ社製）、モデピクスシリーズ（商品名、荒川化学社製）、アデカレジン（商品名、ＡＤＥＫＡ社製）等を挙げることができる。 市 販 A commercial product can be used as the epoxy resin. Commercial products of the epoxy resin include, for example, Watersol series (trade name, manufactured by DIC Corporation), Modepix series (trade name, manufactured by Arakawa Chemical Co., Ltd.), and ADEKARESIN (trade name, manufactured by ADEKA Corporation). it can.
　樹脂粒子（Ａ）としての前記ウレタン樹脂粒子は、一般にポリエステルポリオール、ポリエーテルポリオール等のポリオールとジイソシアネートからなるポリウレタンを必要に応じて、ジオール、ジアミン等のような２個以上の活性水素をもつ低分子量化合物である鎖伸長剤の存在下で鎖伸長し、水中に安定に分散させることにより得られるものであり、公知のものを広く使用することができる。 The urethane resin particles as the resin particles (A) generally include a polyurethane comprising a polyol such as a polyester polyol or a polyether polyol and a diisocyanate, and if necessary, a polyurethane having two or more active hydrogens such as diols and diamines. It is obtained by elongating a chain in the presence of a chain extender that is a molecular weight compound and stably dispersing it in water, and known compounds can be widely used.
　上記ウレタン樹脂の市販品としては、例えばハイドランＨＷ－３３０、同ＨＷ－３４０、同ＨＷ－３５０（いずれも大日本インキ化学工業社製）、スーパーフレックス１００、同１１０、同１５０、同Ｆ－８４３８Ｄ、同４２０（いずれも第一工業製薬社製）、アデカボンタイダーＨＵＸ－２３２、同２６０、同３２０、同３５０（いずれもＡＤＥＫＡ社製）等を挙げることができる。 Commercially available urethane resins include, for example, Hydran HW-330, HW-340, HW-350 (all manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 100, 110, 150, and F-8438D. And 420 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecabon Tyder HUX-232, 260, 320 and 350 (all manufactured by ADEKA), and the like.
＜アクリル樹脂粒子（Ｂ）＞
　アクリル樹脂粒子（Ｂ）は、重量平均分子量が７５００～７５０００、酸価が１０～９０ｍｇＫＯＨ／ｇであるアクリル樹脂粒子である。アクリル樹脂粒子（Ｂ）は、水性塗料組成物において、造膜補助の作用をする樹脂である。具体的には、塗装後の乾燥過程においてアクリル樹脂粒子（Ｂ）が相転移とともに拡散して、基体樹脂である樹脂粒子（Ａ）間の空隙が充填される。このように、乾燥過程における塗膜の空隙形成が抑制されることにより、組成物中に溶剤等の造膜助剤を全く含まないか、含んでも少量のみの含有であっても、低温での造膜性を向上させることができる。 <Acrylic resin particles (B)>
The acrylic resin particles (B) are acrylic resin particles having a weight average molecular weight of 7,500 to 75,000 and an acid value of 10 to 90 mgKOH / g. The acrylic resin particles (B) are resins that act to assist film formation in the aqueous coating composition. Specifically, in the drying process after coating, the acrylic resin particles (B) diffuse together with the phase transition and fill the voids between the resin particles (A) as the base resin. As described above, since the formation of voids in the coating film during the drying process is suppressed, the composition does not contain any film-forming aid such as a solvent at all, or even if it contains only a small amount, even at a low temperature. The film forming property can be improved.
　アクリル樹脂粒子（Ｂ）は、前記樹脂粒子（Ａ）中で、詳述したアクリル樹脂粒子と同様の重合法を用い、重合条件を適宜変更することで得ることができる。 The acrylic resin particles (B) can be obtained by using the same polymerization method as the acrylic resin particles described in detail in the resin particles (A) and appropriately changing the polymerization conditions.
　アクリル樹脂粒子（Ｂ）は、分子量調整の観点から、有機溶媒中で前述の重合性不飽和モノマーを溶液重合法で重合して共重合体を得た後に水分散して樹脂粒子とする方法で製造したものを好適に使用することができる。 From the viewpoint of controlling the molecular weight, the acrylic resin particles (B) are obtained by polymerizing the aforementioned polymerizable unsaturated monomer in an organic solvent by a solution polymerization method to obtain a copolymer, and then dispersing in water to obtain resin particles. The manufactured product can be suitably used.
　アクリル樹脂粒子（Ｂ）の重量平均分子量は７５００～７５０００であり、好ましくは９０００以上、より好ましくは１００００以上、また、好ましくは６００００以下、より好ましくは４００００以下である。 (4) The weight average molecular weight of the acrylic resin particles (B) is 7500 to 75,000, preferably 9000 or more, more preferably 10,000 or more, and preferably 60,000 or less, more preferably 40,000 or less.
　重量平均分子量を７５００以上とすることにより、防食性や硬度を良好なものとすることができる。また重量平均分子量を７５０００以下とすることにより、十分な拡散性が得られ、良好な造膜性となる。 こ と By setting the weight average molecular weight to 7,500 or more, good anticorrosion property and hardness can be obtained. Further, by setting the weight average molecular weight to 75,000 or less, sufficient diffusibility is obtained, and good film-forming properties are obtained.
　アクリル樹脂粒子（Ｂ）の酸価は、１０～９０ｍｇＫＯＨ／ｇであり、好ましくは２０ｍｇＫＯＨ／ｇ以上、より好ましくは３０ｍｇＫＯＨ／ｇ以上、また、好ましくは８０ｍｇＫＯＨ／ｇ以下、より好ましくは７０ｍｇＫＯＨ／ｇ以下である。 The acid value of the acrylic resin particles (B) is 10 to 90 mgKOH / g, preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g or less. It is.
　酸価を１０ｍｇＫＯＨ／ｇ以上とすることにより、分散安定性が良好となる。また酸価を９０ｍｇＫＯＨ／ｇ以下とすることにより、耐水性が良好となり、十分な防食性が得られる。 (4) By setting the acid value to 10 mgKOH / g or more, the dispersion stability is improved. Further, by setting the acid value to 90 mgKOH / g or less, the water resistance becomes good, and a sufficient anticorrosion property is obtained.
　本明細書において酸価（ｍｇＫＯＨ／ｇ）は、試料１ｇ（樹脂の場合は固形分１ｇ）に含まれる酸基の量を水酸化カリウムに換算したときの水酸化カリウムのｍｇ数で表したものである。水酸化カリウムの分子量は５６．１とする。 In the present specification, the acid value (mgKOH / g) is represented by mg of potassium hydroxide when the amount of acid groups contained in 1 g of a sample (1 g of solid content in the case of resin) is converted into potassium hydroxide. It is. The molecular weight of potassium hydroxide is 56.1.
　酸価の測定は、ＪＩＳ　Ｋ－５６０１－２－１（１９９９）に準拠して行う。試料をトルエン／エタノール＝２／１（体積比）の混合溶剤で溶解し、フェノールフタレインを指示薬として水酸化カリウム溶液で滴定し、下記式により算出する。 (4) The acid value is measured in accordance with JIS K-5601-2-1 (1999). A sample is dissolved in a mixed solvent of toluene / ethanol = 2/1 (volume ratio), titrated with a potassium hydroxide solution using phenolphthalein as an indicator, and calculated by the following equation.
　酸価（ｍｇＫＯＨ／ｇ）＝５６．１×Ｖ×Ｃ／ｍ
　Ｖ：滴定量（ｍｌ）、Ｃ：滴定液の濃度（ｍｏｌ／ｌ）、ｍ：試料の固形分重量（ｇ） Acid value (mgKOH / g) = 56.1 × V × C / m
V: titration (ml), C: concentration of titrant (mol / l), m: solid weight of sample (g)
　アクリル樹脂粒子（Ｂ）のガラス転移温度（Ｔｇ）は、０℃以上が好ましく、１０℃以上がより好ましく、２０℃以上がさらに好ましい。
　ガラス転移温度（Ｔｇ）を０℃以上とすることにより、得られる塗膜の硬度の低下を防ぐことができる。 The glass transition temperature (Tg) of the acrylic resin particles (B) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, even more preferably 20 ° C. or higher.
By setting the glass transition temperature (Tg) to 0 ° C. or higher, a decrease in hardness of the obtained coating film can be prevented.
　なお本明細書において、樹脂が２種以上のモノマーからなる共重合体である場合には、当該共重合体のガラス転移温度（Ｔｇ、℃）は、下記式によって算出することができる。 In this specification, when the resin is a copolymer composed of two or more monomers, the glass transition temperature (Tg, ° C) of the copolymer can be calculated by the following equation.
　１／Ｔｇ（Ｋ）＝（Ｗ１／Ｔ１）＋（Ｗ２／Ｔ２）＋・・（Ｗｎ／Ｔｎ）
　Ｔｇ（℃）＝Ｔｇ（Ｋ）－２７３
　各式中、ｎは使用されたモノマーの種類数（自然数）を表し、Ｗ１～Ｗｎは共重合に使用されたｎ種のモノマーのそれぞれの重量％、Ｔ１～Ｔｎはｎ種の単量体のホモポリマーのそれぞれのＴｇ（Ｋ）を表わす。なお、Ｔ１～Ｔｎは、Ｐｏｌｙｍｅｒ　Ｈａｎｄ　Ｂｏｏｋ（Ｓｅｃｏｎｄ　Ｅｄｉｔｉｏｎ，Ｊ．Ｂｒａｎｄｕｐ・Ｅ．Ｈ．Ｉｍｍｅｒｇｕｔ編）ＩＩＩ－１３９～１７９頁に記載された値を用いることができる。
　また、モノマーのホモポリマーのＴｇが明確でない場合のガラス転移温度（℃）は、実測により静的ガラス転移温度として求めることもできる。この場合、例えば示差走査熱量計「ＤＳＣ－２２０Ｕ」（セイコーインスツルメント社製）を用いて、試料を測定カップに採り、真空吸引して完全に溶剤を除去した後、３℃／分の昇温速度で－２０℃～＋２００℃の範囲で熱量変化を測定し、低温側の最初のベースラインの変化点を静的ガラス転移温度とする。 1 / Tg (K) = (W1 / T1) + (W2 / T2) +... (Wn / Tn)
Tg (° C.) = Tg (K) -273
In each formula, n represents the number of types of monomers used (natural number), W1 to Wn are the weight percentages of the n monomers used in the copolymerization, and T1 to Tn are the weights of the n monomers. Represents the respective Tg (K) of the homopolymer. For T1 to Tn, the values described in Polymer Hand Book (Second Edition, edited by J. Brandup, EH Immergut), pages III-139 to 179, can be used.
Further, the glass transition temperature (° C.) when the Tg of the homopolymer of the monomer is not clear can also be obtained as a static glass transition temperature by actual measurement. In this case, for example, using a differential scanning calorimeter “DSC-220U” (manufactured by Seiko Instruments Inc.), a sample is taken in a measuring cup, and the solvent is completely removed by vacuum suction. The calorie change is measured at a temperature rate in the range of −20 ° C. to + 200 ° C., and the first baseline change point on the low temperature side is defined as a static glass transition temperature.
　アクリル樹脂粒子（Ｂ）の最低造膜温度は１０℃未満が好ましく、７．５℃以下がより好ましく、５℃以下がさらに好ましい。最低造膜温度を１０℃未満とすることにより、造膜性の低下を防ぎ、良好な防食性を実現できる。 最低 The minimum film-forming temperature of the acrylic resin particles (B) is preferably less than 10 ° C, more preferably 7.5 ° C or less, and even more preferably 5 ° C or less. By setting the minimum film-forming temperature to less than 10 ° C., it is possible to prevent a decrease in film-forming properties and to realize good corrosion protection.
　アクリル樹脂粒子（Ｂ）のＳＰ値（溶解性パラメータ値）は９．３以下が好ましく、９．０以下がより好ましい。上記ＳＰ値を９．３以下とすることにより、耐水性が良好となり、防食性も優れたものとなる。 ＳＰ The SP value (solubility parameter value) of the acrylic resin particles (B) is preferably 9.3 or less, more preferably 9.0 or less. By setting the SP value to 9.3 or less, the water resistance becomes good, and the anticorrosion becomes excellent.
　また、樹脂粒子（Ａ）の最外層（最も外側の表層部分）とアクリル樹脂粒子（Ｂ）とのＳＰ値差は、０．３以内が好ましく、０．２以内がより好ましく、０．１以内がさらに好ましい。上記ＳＰ値差を０．３以内とすることにより相溶性が良好で、拡散性も良好となり、優れた防食性となる。 Also, the SP value difference between the outermost layer (outermost surface layer portion) of the resin particles (A) and the acrylic resin particles (B) is preferably within 0.3, more preferably within 0.2, and preferably within 0.1. Is more preferred. When the SP value difference is within 0.3, the compatibility is good, the diffusivity is good, and the corrosion resistance is excellent.
　本明細書において、溶解性パラメーター値（ＳＰ値）は、Ｐｏｌｙｍｅｒ　Ｅｎｇｉｎｅｅｒｉｎｇ　ａｎｄ　Ｓｃｉｅｎｃｅ，１４，Ｎｏ．２，ｐ．１４７（１９７４）に記載された、下記のＦｅｄｏｒｓ式により算出される値である。 に お い て In the present specification, the solubility parameter value (SP value) is as defined in Polymer {Engineering and} Science, 14, No. 2, p. 147 (1974), calculated by the following Fedors equation.
　ＳＰ＝√｛Σ（Δｅ１）／Σ（Δｖ１）｝
（式中、Δｅ１は各単位官能基当たりの凝集エネルギー、Δｖ１は各単位官能基当たりの分子容を示す。）なお、共重合体又は２種以上の樹脂の混合物であるブレンド物のＳＰ値は、単量体ユニット又はブレンド物の各成分のＳＰ値に質量分率を乗じたものを合計した値とした。 SP = {(Δe1) / {(Δv1)}
(In the formula, Δe1 represents the aggregation energy per unit functional group, and Δv1 represents the molecular volume per unit functional group.) The SP value of a copolymer or a blend of a mixture of two or more resins is as follows: , And a value obtained by multiplying the SP value of each component of the monomer unit or the blend by the mass fraction.
　また、アクリル樹脂粒子（Ｂ）の平均粒子径は、５００ｎｍ以下が好ましく、４００ｎｍ以下がより好ましく、３００ｎｍ以下がさらに好ましい。 The average particle size of the acrylic resin particles (B) is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
　平均粒子径を５００ｎｍ以下とすることにより、分散安定性が良好で、また、拡散性の良好となることから、優れた防食性が実現される。 By setting the average particle diameter to 500 nm or less, the dispersion stability is good and the diffusivity is good, so that excellent corrosion protection is realized.
　水性塗料組成物において、樹脂粒子（Ａ）及びアクリル樹脂粒子（Ｂ）の固形分総量に対して、樹脂粒子（Ａ）の固形分総量は３５～９０質量％であり、アクリル樹脂粒子（Ｂ）の固形分総量は１０～６５質量％である。固形分総量は、樹脂粒子（Ａ）が４０質量％以上、アクリル樹脂粒子（Ｂ）が６０質量％以下が好ましく、樹脂粒子（Ａ）が４５質量％以上、アクリル樹脂粒子（Ｂ）が５５質量％以下がより好ましく、また、樹脂粒子（Ａ）が８０質量％以下、アクリル樹脂粒子（Ｂ）が２０質量％以上が好ましく、樹脂粒子（Ａ）が７０質量％以下、アクリル樹脂粒子（Ｂ）が３０質量％以上がより好ましい。 In the aqueous coating composition, the total solid content of the resin particles (A) is 35 to 90% by mass based on the total solid content of the resin particles (A) and the acrylic resin particles (B), and the acrylic resin particles (B) Has a total solid content of 10 to 65% by mass. The total solid content is preferably 40% by mass or more of resin particles (A) and 60% by mass or less of acrylic resin particles (B), 45% by mass or more of resin particles (A) and 55% by mass of acrylic resin particles (B). %, More preferably 80% by mass or less of the resin particles (A), 20% by mass or more of the acrylic resin particles (B), 70% by mass or less of the resin particles (A), and the acrylic resin particles (B). Is more preferably 30% by mass or more.
　樹脂粒子（Ａ）及びアクリル樹脂粒子（Ｂ）の固形分総量に対して、樹脂粒子（Ａ）の固形分総量を９０質量％以下、アクリル樹脂粒子（Ｂ）の固形分総量を１０質量％以上とすることにより、得られる塗膜の造膜性が良好なものとなる。また、樹脂粒子（Ａ）の固形分総量を３５質量％以上、アクリル樹脂粒子（Ｂ）の固形分総量を６５質量％以下とすることにより、得られる塗膜の防食性が良好なものとなる。 The total solid content of the resin particles (A) is 90% by mass or less, and the total solid content of the acrylic resin particles (B) is 10% by mass or more based on the total solid content of the resin particles (A) and the acrylic resin particles (B). By doing so, the film forming properties of the obtained coating film become favorable. Further, by setting the total solid content of the resin particles (A) to 35% by mass or more and the total solid content of the acrylic resin particles (B) to 65% by mass or less, the obtained coating film has good corrosion resistance. .
　水性塗料組成物は、樹脂粒子（Ａ）とアクリル樹脂粒子（Ｂ）との混合物であるが、それらの混合方法において制限はない。すなわち、樹脂粒子（Ａ）にアクリル樹脂粒子（Ｂ）を添加する方法と、アクリル樹脂粒子（Ｂ）に樹脂粒子（Ａ）を添加する方法のどちらも採用することができる。 The aqueous coating composition is a mixture of the resin particles (A) and the acrylic resin particles (B), but there is no limitation in the method of mixing them. That is, both a method of adding the acrylic resin particles (B) to the resin particles (A) and a method of adding the resin particles (A) to the acrylic resin particles (B) can be adopted.
　また、アクリル樹脂粒子（Ｂ）を保護コロイドとして用い共重合させて水性エマルションを合成し、結果的に樹脂粒子（Ａ）とアクリル樹脂粒子（Ｂ）とが共存する組成物とする方法を採用することもできる。 Further, a method is employed in which an acrylic resin particle (B) is used as a protective colloid and copolymerized to synthesize an aqueous emulsion, resulting in a composition in which the resin particle (A) and the acrylic resin particle (B) coexist. You can also.
　水性塗料組成物は、塗料の貯蔵安定性の観点から、ｐＨが５．０以上が好ましく、６．０以上がより好ましく、また、１０．０以下が好ましく、９．０以下がより好ましい。 From the viewpoint of the storage stability of the paint, the aqueous paint composition preferably has a pH of 5.0 or more, more preferably 6.0 or more, and preferably 10.0 or less, more preferably 9.0 or less.
　また、水性塗料組成物は、必要に応じて、架橋剤、硬化触媒、着色顔料等の顔料、充填剤、骨材、分散剤、湿潤剤、増粘剤、レオロジーコントロール剤、表面調整剤、消泡剤、防腐剤、防黴剤、ｐＨ調整剤、防錆剤、沈降防止剤、凍結防止剤、皮張り防止剤、紫外線吸収剤、酸化防止剤、有機溶剤等を含有させることもできる。 In addition, the aqueous coating composition may contain a crosslinking agent, a curing catalyst, a pigment such as a coloring pigment, a filler, an aggregate, a dispersant, a wetting agent, a thickener, a rheology control agent, a surface conditioning agent, Foaming agents, preservatives, fungicides, pH adjusters, rust inhibitors, anti-settling agents, anti-freezing agents, anti-skinning agents, ultraviolet absorbers, antioxidants, organic solvents and the like can also be included.
　水性塗料組成物は、必要に応じて下地処理した各種基材上、好ましくは金属基材上に塗装して硬化した硬化塗膜とすることが好ましい。塗装は、従来公知の方法、例えばローラー塗装、スプレー塗装、刷毛塗装、カーテン塗装、シャワー塗装、浸漬塗装等の方法によって直接１回又は２回以上塗装して塗膜を形成することができる。 It is preferable that the water-based coating composition is a cured coating film which is applied and cured on various substrates, preferably a metal substrate, as required. The coating can be applied once or twice or more by a conventionally known method such as roller coating, spray coating, brush coating, curtain coating, shower coating, dip coating, etc. to form a coating film.
　基材を金属基材とした場合、当該金属基材上に本実施形態に係る水性塗料組成物を塗装、硬化して硬化塗膜を形成することにより、低温での造膜性が良好で、防食性にも優れる塗装物品を得ることができる。 When the base material is a metal base material, the water-based coating composition according to the present embodiment is applied on the metal base material, and cured to form a cured coating film. A coated article having excellent anticorrosion properties can be obtained.
　水性塗料組成物の塗膜は、省エネルギー等の観点から常温で硬化させることが好ましい。なお、生産効率向上等の観点から、強制乾燥や加熱硬化させることもできる。
　また、水性塗料組成物を塗装して得られる硬化塗膜の膜厚は、形成される硬化塗膜の防食性、耐水性及び硬度等の観点から、１０μｍ以上が好ましく、２０μｍ以上がより好ましく、２５μｍ以上がさらに好ましく、また、２００μｍ以下が好ましく、１００μｍ以下がより好ましく、６０μｍ以下がさらに好ましい。 The coating film of the aqueous coating composition is preferably cured at room temperature from the viewpoint of energy saving and the like. In addition, from the viewpoint of improving the production efficiency, forced drying or heat curing can also be performed.
In addition, the thickness of the cured coating film obtained by applying the aqueous coating composition is preferably 10 μm or more, more preferably 20 μm or more, from the viewpoints of corrosion resistance, water resistance, hardness, and the like of the formed cured coating film. 25 μm or more is further preferable, 200 μm or less is preferable, 100 μm or less is more preferable, and 60 μm or less is further preferable.
　以下、製造例、実施例及び比較例を挙げて、本発明をさらに具体的に説明する。但し、本発明は、これらにより限定されない。各例において、「部」及び「％」は、特記しない限り、質量基準による。また、塗膜の膜厚は硬化塗膜に基づくものである。なお、表中の空欄は、その成分が含まれていないことを表す。 Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. However, the present invention is not limited by these. In each example, “parts” and “%” are based on mass unless otherwise specified. Further, the thickness of the coating film is based on the cured coating film. Note that a blank column in the table indicates that the component is not included.
＜樹脂粒子（Ａ）の製造＞
　製造例１
　撹拌機、温度計、還流凝縮機を備えた重合装置中に、表１に示す量の仕込みの脱イオン水及びＮｅｗｃｏｌ（登録商標）７０７ＳＦ（商品名、日本乳化剤社製、アニオン性界面活性剤、固形分３０質量％）を入れ、窒素置換を十分に行った後、昇温した。約１００ｒｐｍで撹拌しながら内温を８２℃に保ち、表１に示される（Ａ１）成分をホモミキサーを用いて乳化したもの（以下、（Ａ１）成分乳化物という。（Ａ２）成分、（Ｂ１）成分及び（Ｂ２）成分についても同様に表記する。）、及び開始剤１水溶液（表１中、ＶＡ－０５７は商品名、富士フィルム和光純薬社製、２－２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンジアミン］四水塩）を３時間かけて滴下し、重合させた。滴下終了後、８２℃で０．５時間反応させ、開始剤２水溶液を０．５時間かけて滴下した。滴下終了後、８２℃で１．５時間反応させ、その後２５℃に冷却した。最後に表１に示す中和剤を添加し、固形分濃度４０．０質量％の樹脂粒子（Ａ－１）（最外層のＳＰ値９．０１、重量平均分子量約１６万、最低造膜温度１５℃）のエマルションを得た。 <Production of resin particles (A)>
Production Example 1
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, charged amounts of deionized water and Newcol (registered trademark) 707SF (trade name, manufactured by Nippon Emulsifier, anionic surfactant, (Solid content: 30% by mass), and after sufficiently purging with nitrogen, the temperature was raised. An emulsion obtained by emulsifying the component (A1) shown in Table 1 using a homomixer while maintaining the internal temperature at 82 ° C. while stirring at about 100 rpm (hereinafter, referred to as a component (A1) emulsion. The component (A2) and the component (B1) ) Component and (B2) component), and an aqueous solution of initiator 1 (in Table 1, VA-057 is a trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 2-2'-azobis [N- (2-carboxyethyl) -2-methylpropiondiamine] tetrahydrate) was added dropwise over 3 hours to polymerize. After the completion of the dropwise addition, the reaction was carried out at 82 ° C. for 0.5 hour, and the initiator 2 aqueous solution was added dropwise over 0.5 hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C for 1.5 hours, and then cooled to 25 ° C. Finally, the neutralizing agent shown in Table 1 was added, and the resin particles (A-1) having a solid content of 40.0% by mass (SP value of the outermost layer: 9.01, weight average molecular weight: about 160,000, minimum film forming temperature: 15 ° C.).
　上記エマルションは、粘度（Ｂ型粘度計にて測定、６０ｒｐｍ、２０℃）４２０ｍＰａ・ｓ、ｐＨ９．２（ｐＨメーターにて測定）、平均粒子径１３０ｎｍであった。 The emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 420 mPa · s, a pH of 9.2 (measured with a pH meter), and an average particle diameter of 130 nm.
　製造例２
　撹拌機、温度計、還流凝縮機を備えた重合装置中に、表１に示す量の仕込みの脱イオン水及びＮｅｗｃｏｌ７０７ＳＦを入れ、窒素置換を十分に行った後、昇温した。約１００ｒｐｍで撹拌しながら内温を８２℃に保ち、表１に示される（Ａ１）成分をホモミキサーを用いて乳化したもの、及び開始剤１水溶液を滴下開始し、重合させた。滴下速度は、（Ａ１）成分乳化物は約１４６．０部／時間、開始剤１水溶液は約６．６部／時間とした。（Ａ１）成分乳化物を滴下終了すると同時に、表１に示す（Ｂ２）成分乳化物を滴下し始め、約１４６．０部／時間で滴下した。滴下終了後、８２℃で０．５時間反応させ、開始剤２水溶液を約３．３部／時間で滴下した。滴下終了後、８２℃で１．５時間反応させ、その後２５℃に冷却した。最後に表１に示す中和剤を添加し、固形分濃度４０．０質量％の樹脂粒子（Ａ－２）（最外層のＳＰ値９．０３、重量平均分子量約２０万、最低造膜温度２０℃）のエマルションを得た。 Production Example 2
Into a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, charged amounts of deionized water and Newcol 707SF shown in Table 1 were added, and the temperature was raised after sufficient nitrogen replacement. While stirring at about 100 rpm, the internal temperature was maintained at 82 ° C., and the component (A1) shown in Table 1 emulsified using a homomixer and an aqueous solution of initiator 1 were added dropwise to initiate polymerization. The dropping rate was about 146.0 parts / hour for the component (A1) emulsion and about 6.6 parts / hour for the aqueous initiator 1 solution. At the same time when the dropping of the (A1) component emulsion was completed, the dropping of the (B2) component emulsion shown in Table 1 was started, and was dropped at about 146.0 parts / hour. After completion of the dropwise addition, the reaction was carried out at 82 ° C. for 0.5 hour, and an aqueous solution of initiator 2 was added dropwise at about 3.3 parts / hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C for 1.5 hours, and then cooled to 25 ° C. Finally, the neutralizing agent shown in Table 1 was added, and the resin particles (A-2) having a solid content concentration of 40.0% by mass (SP value of the outermost layer: 9.03, weight average molecular weight: about 200,000, minimum film forming temperature) (20 ° C.).
　上記エマルションは、粘度（Ｂ型粘度計にて測定、６０ｒｐｍ、２０℃）４００ｍＰａ・ｓ、ｐＨ９．２（ｐＨメーターにて測定）、平均粒子径１２０ｎｍであった。 The emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 400 mPa · s, a pH of 9.2 (measured with a pH meter), and an average particle size of 120 nm.
　製造例３
　撹拌機、温度計、還流凝縮機を備えた重合装置中に、表１に示す量の仕込みの脱イオン水及びＮｅｗｃｏｌ７０７ＳＦを入れ、窒素置換を十分に行った後、昇温した。約１００ｒｐｍで撹拌しながら内温を８２℃に保ち、表１に示される（Ａ１）成分をホモミキサーを用いて乳化したもの、及び開始剤１水溶液を滴下開始し、重合させた。滴下速度は、（Ａ１）成分乳化物は約１４６．０部／時間、開始剤１水溶液は約６．６部／時間とした。（Ａ１）成分乳化物が滴下終了すると同時に、表１に示す（Ａ２）成分乳化物を滴下し始めた。これと同時に表１に示す（Ｂ１）成分乳化物を（Ａ２）成分乳化物に滴下した。（Ｂ１）成分乳化物の滴下速度は、（Ａ２）成分乳化物の滴下終了と同時に滴下が終了する速度、すなわち本製造例では約７３．０部／時間とした。その後（Ｂ２）成分乳化物を約１４６．０部／時間で滴下した。滴下終了後、８２℃で０．５時間反応させ、開始剤２水溶液を約３．３部／時間で滴下した。滴下終了後、８２℃で１．５時間反応させ、その後２５℃に冷却した。最後に表１に示す中和剤を添加し、固形分濃度４０．０質量％の樹脂粒子（Ａ－３）（最外層のＳＰ値９．０３、重量平均分子量約２２万、最低造膜温度１８℃）のエマルションを得た。 Production Example 3
Into a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, charged amounts of deionized water and Newcol 707SF shown in Table 1 were added, and the temperature was raised after sufficient nitrogen replacement. While stirring at about 100 rpm, the internal temperature was maintained at 82 ° C., and the component (A1) shown in Table 1 emulsified using a homomixer and an aqueous solution of initiator 1 were added dropwise to initiate polymerization. The dropping rate was about 146.0 parts / hour for the component (A1) emulsion and about 6.6 parts / hour for the aqueous initiator 1 solution. At the same time when the dropping of the (A1) component emulsion was completed, the dropping of the (A2) component emulsion shown in Table 1 was started. At the same time, the component (B1) emulsion shown in Table 1 was dropped into the component (A2) emulsion. The dropping rate of the component (B1) emulsion was set to a rate at which the dropping was completed simultaneously with the dropping of the component (A2) emulsion, that is, about 73.0 parts / hour in the present production example. Thereafter, the component (B2) emulsion was dropped at about 146.0 parts / hour. After completion of the dropwise addition, the reaction was carried out at 82 ° C. for 0.5 hour, and an aqueous solution of initiator 2 was added dropwise at about 3.3 parts / hour. After the completion of the dropwise addition, the reaction was carried out at 82 ° C for 1.5 hours, and then cooled to 25 ° C. Finally, a neutralizing agent shown in Table 1 was added, and resin particles (A-3) having a solid content of 40.0% by mass (SP value of the outermost layer: 9.03, weight average molecular weight: about 220,000, minimum film forming temperature) 18 ° C.).
　上記エマルションは、粘度（Ｂ型粘度計にて測定、６０ｒｐｍ、２０℃）７１０ｍＰａ・ｓ、ｐＨ９．２（ｐＨメーターにて測定）、平均粒子径１００ｎｍであった。 The emulsion had a viscosity (measured with a B-type viscometer, 60 rpm, 20 ° C.) of 710 mPa · s, a pH of 9.2 (measured with a pH meter), and an average particle diameter of 100 nm.
　なお、樹脂粒子（Ａ－１）～樹脂粒子（Ａ－３）の最低造膜温度は、各樹脂粒子の固形分総量に対してエチレングリコールモノブチルエーテルを２０質量％添加して測定した値である。 The minimum film forming temperature of the resin particles (A-1) to (A-3) is a value measured by adding 20% by mass of ethylene glycol monobutyl ether to the total solid content of each resin particle. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　製造例４
　温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にエチレングリコールモノブチルエーテル２０部及びプロピレングリコールモノメチルエーテル１４部を仕込み１１５℃に昇温後、スチレン１０部、メチルメタクリレート２０部、ｎ－ブチルアクリレート３０部、ｉ－ブチルメタクリレート３０部、アクリル酸１部、メタクリル酸９部、プロピレングリコールモノメチルエーテル１５部及びパーブチルＯ（登録商標、日油社製、重合開始剤、固形分１００％）５部の混合物を４時間かけて滴下し、滴下終了後１時間熟成した。その後さらにプロピレングリコールモノメチルエーテル５部及びパーブチルＯ８部の混合物を１時間かけて滴下し、滴下終了後１時間熟成した。次いで室温まで冷却することにより、固形分６５質量％のアクリル共重合体１の溶液を得た。得られたアクリル共重合体１は、ＳＰ値９．１２、酸価６６ｍｇＫＯＨ／ｇ、重量平均分子量約２２００であった。 Production Example 4
A reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping device was charged with 20 parts of ethylene glycol monobutyl ether and 14 parts of propylene glycol monomethyl ether, and heated to 115 ° C., and then 10 parts of styrene. 20 parts of methyl methacrylate, 30 parts of n-butyl acrylate, 30 parts of i-butyl methacrylate, 1 part of acrylic acid, 9 parts of methacrylic acid, 15 parts of propylene glycol monomethyl ether and perbutyl O (registered trademark, manufactured by NOF CORPORATION, polymerization initiator) , 100% solids) was added dropwise over 4 hours, and the mixture was aged for 1 hour after completion of the addition. Thereafter, a mixture of 5 parts of propylene glycol monomethyl ether and 8 parts of perbutyl O was added dropwise over 1 hour, and the mixture was aged for 1 hour after completion of the dropwise addition. Then, by cooling to room temperature, a solution of the acrylic copolymer 1 having a solid content of 65% by mass was obtained. The obtained acrylic copolymer 1 had an SP value of 9.12, an acid value of 66 mgKOH / g, and a weight average molecular weight of about 2,200.
　還流管、温度計及び撹拌機を装着した四つ口フラスコに上記アクリル共重合体１の溶液６５部（固形分４２部）、エピコート（登録商標）１００９（商品名、ジャパンエポキシレジン社製、エポキシ樹脂、固形分１００％、エポキシ当量約３５００、重量平均分子量約３９００）５８部及びジエチレングリコールモノブチルエーテル１１．６部及びプロピレングリコールモノメチルエーテル２８．４部を加えて１００℃に加熱して溶解させた後、約２時間反応を行った。その後、アンモニア水（２５％）で当量中和したのち脱イオン水を攪拌添加し、固形分４０質量％の樹脂粒子（Ａ－４）（最外層のＳＰ値９．１２、最低造膜温度３０℃）分散液を得た。 In a four-necked flask equipped with a reflux tube, a thermometer, and a stirrer, 65 parts (solid content: 42 parts) of the acrylic copolymer 1 and Epicoat® 1009 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy After adding 58 parts of resin, 100% solids, epoxy equivalent of about 3500, and weight average molecular weight of about 3900), 11.6 parts of diethylene glycol monobutyl ether and 28.4 parts of propylene glycol monomethyl ether, the mixture was heated to 100 ° C. and dissolved. The reaction was carried out for about 2 hours. Thereafter, the mixture was neutralized with an equivalent amount of aqueous ammonia (25%), and then deionized water was added with stirring. C) A dispersion was obtained.
　得られた樹脂粒子（Ａ－４）は、平均粒子径が２００ｎｍ、酸価が４４ｍｇＫＯＨ／ｇであった。 The obtained resin particles (A-4) had an average particle diameter of 200 nm and an acid value of 44 mgKOH / g.
＜アクリル樹脂粒子（Ｂ）の製造＞
　製造例５
　温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にエチレングリコールモノブチルエーテル２０部とプロピレングリコールモノメチルエーテル１４部を仕込み１１５℃に昇温後、スチレン２０部、ｎ－ブチルアクリレート２０部、メチルメタクリレート１９部、ｉ－ブチルメタクリレート３５部、アクリル酸５部、メタクリル酸１部、プロピレングリコールモノメチルエーテル１５部及び開始剤であるパーブチルＯ７．０部の混合物を４時間かけて滴下し、滴下終了後１時間熟成した。その後さらにプロピレングリコールモノメチルエーテル５部及びパーブチルＯ１．０部の混合物を１時間かけて滴下し、滴下終了後１時間熟成した。得られたアクリル樹脂にアンモニア水（固形分２５％）を加えて、当量中和した後、攪拌しながら脱イオン水を添加して樹脂を分散させた。その後、減圧状態で溶剤であるプロピレングリコールモノメチルエーテルを除去し、再び脱イオン水を添加して固形分３０質量％のアクリル樹脂粒子（Ｂ－１）分散液を得た。得られたアクリル樹脂粒子（Ｂ－１）は重量平均分子量が９０００、酸価が４５．４ｍｇＫＯＨ／ｇ、ガラス転移温度が４１．７℃、ＳＰ値が８．９８、平均粒子径が１８０ｎｍ、最低造膜温度が０℃であった。 <Production of acrylic resin particles (B)>
Production Example 5
20 parts of ethylene glycol monobutyl ether and 14 parts of propylene glycol monomethyl ether were charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping device. A mixture of 20 parts of n-butyl acrylate, 19 parts of methyl methacrylate, 35 parts of i-butyl methacrylate, 5 parts of acrylic acid, 1 part of methacrylic acid, 15 parts of propylene glycol monomethyl ether and 7.0 parts of perbutyl O as an initiator was added for 4 hours. Then, the mixture was aged for 1 hour after completion of the addition. Thereafter, a mixture of 5 parts of propylene glycol monomethyl ether and 1.0 part of perbutyl O was further added dropwise over 1 hour, and the mixture was aged for 1 hour after completion of the addition. Aqueous ammonia (solid content: 25%) was added to the obtained acrylic resin to neutralize it by an equivalent amount, and then deionized water was added with stirring to disperse the resin. Thereafter, the solvent, propylene glycol monomethyl ether, was removed under reduced pressure, and deionized water was added again to obtain a dispersion of acrylic resin particles (B-1) having a solid content of 30% by mass. The obtained acrylic resin particles (B-1) have a weight average molecular weight of 9000, an acid value of 45.4 mg KOH / g, a glass transition temperature of 41.7 ° C., an SP value of 8.98, an average particle diameter of 180 nm, and a minimum of The film formation temperature was 0 ° C.
　製造例６～１５
　製造例５において、配合組成を表２に示すものとする以外は、製造例５と同様にして、各アクリル樹脂粒子（Ｂ－２）～（Ｂ－１１）を得た。開始剤はすべて製造例５と同じくパーブチルＯを使用した（配分比率は製造例５と同じ条件）。得られた各アクリル樹脂粒子の重量平均分子量、酸価、ガラス転移温度、ＳＰ値、平均粒子径及び最低造膜温度（℃）も併せて表２に示す。なお、アクリル樹脂粒子（Ｂ－８）～（Ｂ－１１）は比較例として用いられるものである。 Production Examples 6 to 15
Acrylic resin particles (B-2) to (B-11) were obtained in the same manner as in Production Example 5, except that the composition was changed to that shown in Table 2. All initiators used perbutyl O as in Production Example 5 (allocation ratio was the same as in Production Example 5). Table 2 also shows the weight average molecular weight, acid value, glass transition temperature, SP value, average particle diameter, and minimum film forming temperature (° C.) of each of the obtained acrylic resin particles. The acrylic resin particles (B-8) to (B-11) are used as comparative examples.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
＜水性塗料組成物の製造＞
　実施例１
　ＤＩＳＰＥＲＢＹＫ（登録商標）－１９０（商品名、ＢＹＫ社製、顔料分散剤、固形分４０％）３部（固形分１．２部）、ＢＹＫ（登録商標）－０２４（商品名、ＢＹＫ社製、消泡剤、固形分１００％）０．４部、ＪＲ－６０３（商品名、テイカ社製、酸化チタン、固形分１００％）３５部、スーパーＳＳ（商品名、丸尾カルシウム社製、炭酸カルシウム、固形分１００％）１５部、脱イオン水２５部及びジプロピレングリコールモノメチルエーテル２部を混合しガラスビーズを添加後、ペイントシェーカーで６０分間分散し、顔料ペースト（Ｐ１）（固形分６４．２％）を得た。 <Production of aqueous coating composition>
Example 1
DISPERBYK (registered trademark) -190 (trade name, manufactured by BYK, pigment dispersant, solid content: 40%) 3 parts (solid content: 1.2 parts), BYK (registered trademark) -024 (trade name, manufactured by BYK, 0.4 parts of antifoaming agent, solid content 100%), 35 parts of JR-603 (trade name, manufactured by Teika, titanium oxide, solid content 100%), Super SS (trade name, manufactured by Maruo Calcium Co., calcium carbonate, 15 parts of solid content 100%), 25 parts of deionized water and 2 parts of dipropylene glycol monomethyl ether were mixed, and after adding glass beads, the mixture was dispersed with a paint shaker for 60 minutes to obtain a pigment paste (P1) (solid content of 64.2%). ) Got.
　ガラスビーズを除去後、得られた顔料ペースト（Ｐ１）８０部（固形分５１部）に製造例１で得られた樹脂粒子（Ａ－１）のエマルション１７５部（固形分７０部）、製造例５で得られたアクリル樹脂粒子（Ｂ－１）分散液１００部（固形分３０部）、ＢＹＫ－３４８（商品名、ＢＹＫ社製、表面調整剤、固形分１００％）０．５部及びＳＮシックナー６６０Ｔ（商品名、サンノプコ社製、増粘剤、固形分２０％）２．５部（固形分０．５部）を混合攪拌することにより、ｐＨ８．２、塗料固形分４３質量％の水性塗料組成物Ｎｏ．１を得た。 After removing the glass beads, 175 parts (solid content 70 parts) of the emulsion of the resin particles (A-1) obtained in Production Example 1 were added to 80 parts (solid content 51 parts) of the obtained pigment paste (P1). 100 parts (solid content: 30 parts) of the acrylic resin particle (B-1) dispersion obtained in Step 5, BYK-348 (trade name, manufactured by BYK, surface conditioning agent, solid content: 100%), 0.5 part, and SN Thickener 660T (trade name, manufactured by San Nopco, thickener, solid content 20%) was mixed and stirred with 2.5 parts (solid content 0.5 part) to obtain an aqueous solution having a pH of 8.2 and a paint solid content of 43% by mass. Coating composition No. 1 was obtained.
　実施例２～１２及び比較例１～７
　実施例１において、配合組成を表３及び表４に示すものとする以外は、実施例１と同様にして、各水性塗料組成物Ｎｏ．２～Ｎｏ．１９を得た。 Examples 2 to 12 and Comparative Examples 1 to 7
In the same manner as in Example 1, except that the composition was changed to that shown in Tables 3 and 4, the water-based coating composition No. 2 to No. 19 was obtained.
　ＳＰ値差（樹脂粒子（Ａ）の最外層とアクリル樹脂粒子（Ｂ）のＳＰ値差）も併せて表３及び表４に示す。 ３SP value difference (SP value difference between the outermost layer of resin particles (A) and acrylic resin particles (B)) is also shown in Tables 3 and 4.
　試験板の作製
　研磨及び脱脂を行った７０ｍｍ×１５０ｍｍ×０．８ｍｍの冷間圧延鋼板上に、上記の実施例１～１２及び比較例１～７で得た各水性塗料組成物Ｎｏ．１～Ｎｏ．１９を、エアスプレーを用いて、硬化膜厚４０μｍとなるようにそれぞれ塗装した。次に、２３℃、６５％ＲＨで７日間放置して鋼板上に硬化塗膜が形成された各試験板を得た。 Preparation of Test Plate Each of the aqueous coating composition Nos. Obtained in Examples 1 to 12 and Comparative Examples 1 to 7 above was polished and degreased on a 70 mm × 150 mm × 0.8 mm cold-rolled steel plate. 1 to No. 19 was applied using an air spray so as to have a cured film thickness of 40 μm. Next, each test plate having a cured coating film formed on a steel plate was obtained by being left at 23 ° C. and 65% RH for 7 days.
　試験板の評価
　得られた各試験板について、下記の各試験を行った。評価結果を表３及び表４に併せて示す。 Evaluation of Test Plate Each of the obtained test plates was subjected to the following tests. The evaluation results are shown in Tables 3 and 4.
　防食性：各試験板について、基材に達するように塗膜にナイフでクロスカット傷を入れ、ＪＩＳ　Ｋ　５６００－７－１（１９９９）「耐中性塩水噴霧性」に準拠して、１２０時間耐塩水噴霧試験を行った。ナイフ傷からの錆及びフクレの幅によって以下の基準で評価した。錆及びフクレの最大幅が小さいほど防食性が優れ、評価がＡ～Ｃであれば、防食性が良好である。 Corrosion resistance: With respect to each test plate, the coating film was cut with a knife to reach the base material with a knife, and 120 hours in accordance with JIS K 5600-7-1 (1999) "Neutral salt spray resistance" A salt spray test was performed. Evaluation was made according to the following criteria based on the width of rust and blisters from knife scratches. The smaller the maximum width of rust and blisters, the better the anticorrosion. If the rating is A to C, the anticorrosion is good.
　Ａ：錆、フクレの最大幅が、カット部から１ｍｍ未満（片側）
　Ｂ：錆、フクレの最大幅が、カット部から１ｍｍ以上２ｍｍ未満（片側）
　Ｃ：錆、フクレの最大幅が、カット部から２ｍｍ以上３ｍｍ未満（片側）
　Ｄ：錆、フクレの最大幅が、カット部から３ｍｍ以上５ｍｍ未満（片側）
　Ｅ：錆、フクレの最大幅が、カット部から５ｍｍ以上（片側） A: The maximum width of rust and blisters is less than 1 mm from the cut part (one side)
B: The maximum width of rust and blisters is 1 mm or more and less than 2 mm from the cut part (one side)
C: The maximum width of rust and blisters is 2 mm or more and less than 3 mm from the cut part (one side)
D: The maximum width of rust and blisters is 3 mm or more and less than 5 mm from the cut part (one side)
E: The maximum width of rust and blisters is 5 mm or more from the cut part (one side)
　耐水性：各試験板を２３℃の脱イオン水に４８時間浸漬し、塗面を以下の基準で評価した。評価が◎又は○であれば、耐水性が良好である。
　◎：良好で問題ない。
　○：ややツヤビケが見られるが実用レベルである。
　△：フクレ、ツヤビケのいずれかが認められる。
　×：フクレ、ツヤビケのいずれかが著しく認められる。 Water resistance: Each test plate was immersed in deionized water at 23 ° C. for 48 hours, and the coated surface was evaluated according to the following criteria. If the evaluation is ◎ or ○, the water resistance is good.
A: Good and no problem.
：: Some gloss is observed, but it is at a practical level.
Δ: Either blister or gloss was observed.
×: Either blisters or glossiness are remarkably observed.
　光沢：各試験板について、ＪＩＳ　Ｋ　５６００－４－７（１９９９）「鏡面光沢度」に準拠して、塗面の鏡面光沢度（６０°）を測定した。塗面の鏡面光沢度（６０°）が７０以上であれば、光沢が良好である。 Gloss: For each test plate, the specular gloss (60 °) of the coated surface was measured in accordance with JIS K 5600-4-7 (1999) “Specular gloss”. If the specular gloss (60 °) of the coated surface is 70 or more, the gloss is good.
　鉛筆硬度：各試験板について、ＪＩＳ　Ｋ　５６００－５－４（１９９９）「引っかき硬度（鉛筆法）」に準拠して、塗面の鉛筆硬度を測定した。鉛筆硬度は硬い方から順にＦ、ＨＢ、Ｂ、２Ｂであり、がＢ以上の硬度であれば、硬度が良好である。 Pencil hardness: The pencil hardness of the coated surface of each test plate was measured in accordance with JIS K 5600-5-4 (1999) “Scratch hardness (pencil method)”. Pencil hardness is F, HB, B, 2B in order from the harder one. If the hardness is B or more, the hardness is good.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１８年７月２７日出願の日本特許出願（特願２０１８－１４１５６８）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application (No. 2018-141568) filed on Jul. 27, 2018, the contents of which are incorporated herein by reference.
　本発明によれば、低温での造膜性が良好で、かつ防食性等の塗膜性能にも優れる水性塗料組成物を提供することができる。 According to the present invention, it is possible to provide a water-based coating composition having good film-forming properties at low temperatures and excellent coating properties such as anticorrosion properties.

Claims (5)

  1. 　樹脂粒子（Ａ）及びアクリル樹脂粒子（Ｂ）を含有する組成物であって、
    　前記樹脂粒子（Ａ）は前記アクリル樹脂粒子（Ｂ）とは異なり、
    　前記アクリル樹脂粒子（Ｂ）は重量平均分子量が７５００～７５０００、かつ酸価が１０～９０ｍｇＫＯＨ／ｇであり、
    　前記樹脂粒子（Ａ）及び前記アクリル樹脂粒子（Ｂ）の固形分総量に対して、前記樹脂粒子（Ａ）の固形分総量が３５～９０重量％、かつ前記アクリル樹脂粒子（Ｂ）の固形分総量が１０～６５重量％である水性塗料組成物。     A composition containing resin particles (A) and acrylic resin particles (B),
    The resin particles (A) are different from the acrylic resin particles (B),
    The acrylic resin particles (B) have a weight average molecular weight of 7500 to 75000 and an acid value of 10 to 90 mgKOH / g,
    The total solid content of the resin particles (A) is 35 to 90% by weight based on the total solid content of the resin particles (A) and the acrylic resin particles (B), and the solid content of the acrylic resin particles (B) is An aqueous coating composition having a total amount of 10 to 65% by weight.
  2. 　前記アクリル樹脂粒子（Ｂ）のガラス転移温度が０℃以上である請求項１に記載の水性塗料組成物。 The aqueous coating composition according to claim 1, wherein the acrylic resin particles (B) have a glass transition temperature of 0 ° C or higher.
  3. 　前記樹脂粒子（Ａ）の最外層と前記アクリル樹脂粒子（Ｂ）のＳＰ値差が０．３以内である請求項１又は２に記載の水性塗料組成物。 The aqueous coating composition according to claim 1 or 2, wherein the SP value difference between the outermost layer of the resin particles (A) and the acrylic resin particles (B) is within 0.3.
  4. 　基材と、前記基材上に請求項１～３のいずれか一項に記載の水性塗料組成物の硬化塗膜とを有する塗装物品。 (4) A coated article having a base material and a cured coating film of the aqueous coating composition according to any one of claims 1 to 3 on the base material.
  5. 　前記基材が金属基材である請求項４に記載の塗装物品。 The coated article according to claim 4, wherein the base material is a metal base material.
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