WO2020022073A1 - Composition de revêtement aqueuse - Google Patents

Composition de revêtement aqueuse 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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Prior art keywords
resin particles
acrylic resin
meth
coating composition
solid content
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PCT/JP2019/027439
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English (en)
Japanese (ja)
Inventor
岳 富森
勇 小金井
麗了 江森
兼基 石田
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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 JP2020532283A priority Critical patent/JP7381466B2/ja
Priority to CN201980045138.4A priority patent/CN112424298A/zh
Publication of WO2020022073A1 publication Critical patent/WO2020022073A1/fr

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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.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement aqueuse présentant de bonnes propriétés filmogènes à basses températures, tout en présentant d'excellentes propriétés anti-corrosion. L'invention concerne une composition de revêtement aqueuse contenant des particules de résine (A) et des particules de résine acrylique (B), et configurée de sorte que : les particules de résine (A) soient différentes des particules de résine acrylique (B) ; les particules de résine acrylique (B) présentent une masse moléculaire moyenne en poids de 7 500 à 75 000 et une valeur acide de 10 mgKOH/g à 90 mgKOH/g ; et le rapport entre la quantité totale de teneur en solide dans les particules de résine (A) et la quantité totale de teneur en solide dans les particules de résine acrylique (B) soit de 35:65 à 90:10.
PCT/JP2019/027439 2018-07-27 2019-07-11 Composition de revêtement aqueuse WO2020022073A1 (fr)

Priority Applications (2)

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JP2020532283A JP7381466B2 (ja) 2018-07-27 2019-07-11 水性塗料組成物及び塗装物品
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