WO2021066055A1 - Two-part coating material composition and coated article - Google Patents

Two-part coating material composition and coated article Download PDF

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Publication number
WO2021066055A1
WO2021066055A1 PCT/JP2020/037276 JP2020037276W WO2021066055A1 WO 2021066055 A1 WO2021066055 A1 WO 2021066055A1 JP 2020037276 W JP2020037276 W JP 2020037276W WO 2021066055 A1 WO2021066055 A1 WO 2021066055A1
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Prior art keywords
coating composition
coating film
coating
main agent
component
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PCT/JP2020/037276
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French (fr)
Japanese (ja)
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WO2021066055A8 (en
Inventor
聡 齋藤
晃司 山田
弘二 吉川
貴公 井上
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大日本塗料株式会社
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Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Priority to JP2021551407A priority Critical patent/JP7075545B2/en
Priority to CN202080067946.3A priority patent/CN114450363B/en
Publication of WO2021066055A1 publication Critical patent/WO2021066055A1/en
Publication of WO2021066055A8 publication Critical patent/WO2021066055A8/en

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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a two-component coating composition and a water-based coating composition, a coating film and a coating material obtained from the two-component coating composition.
  • a plastic molded product is a molded product of a polymer substance having plasticity, and is used for mobile phones, home appliances, OA equipment, etc., and the surface of the plastic molded product is decorated or given a function. May be painted to. Therefore, the paint for painting plastic (paint for plastic) not only decorates, but also has abrasion resistance, discoloration resistance, skin oil resistance, and high gloss resistance, depending on the application of the plastic molded product. It may be required to impart functions such as high weather resistance and electrical insulation.
  • lactic acid which is a component of sweat, hand cream, sunscreen, sun oil, etc. It is required to have excellent resistance (lactic acid resistance) and resistance to oleic acid (oleic acid resistance), which is a component contained in sebum.
  • oleic acid resistance resistance to oleic acid
  • solvent-based lacquer paints and solvent-based two-component curable urethane paints have been used as paints for automobile interiors.
  • environmental regulations have become stricter, the paint industry is shifting from solvent-based paints that use organic solvents to water-based paints that use water.
  • a coating film having sufficient lactic acid resistance and olein acid resistance could not be obtained.
  • An object of the present invention is to provide an aqueous coating composition capable of forming a coating film having excellent lactic acid resistance and olein acid resistance.
  • the above problem is the molar ratio of the hydroxyl group (OH) in the main agent and the isocyanate group (NCO) in the curing agent of the main agent containing polycarbonate polyurethane, polyester resin and water and the curing agent containing a hydrophilic polyisocyanate compound. It was found that this can be solved by blending so that is in a specific range. That is, the present invention relates to the following [1] to [14].
  • a two-component coating composition containing a main agent and a curing agent.
  • the main agent contains (A) polycarbonate-based polyurethane, (B) polyester resin, and water, and the (A) polycarbonate-based polyurethane has an average particle size of 0.01 to 0.1 ⁇ m, and the (B) The polyester resin has an average particle size of 0.01 ⁇ m or less and has an average particle size of 0.01 ⁇ m or less.
  • the curing agent contains (C) a hydrophilic polyisocyanate compound.
  • the molar ratio NCO / OH of the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound and the hydroxyl group (OH) in the (A) polycarbonate-based polyurethane and the (B) polyester resin is 1.6 to. 2.0 Two-component paint composition.
  • the present invention is a two-component coating composition containing a main agent and a curing agent.
  • the main agent contains (A) polycarbonate-based polyurethane, (B) polyester resin, and water, and the (A) polycarbonate-based polyurethane has an average particle size of 0.01 to 0.1 ⁇ m, and the (B) The polyester resin has an average particle size of 0.01 ⁇ m or less and has an average particle size of 0.01 ⁇ m or less.
  • the curing agent contains (C) a hydrophilic polyisocyanate compound.
  • the molar ratio NCO / OH of the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound and the hydroxyl group (OH) in the (A) polycarbonate-based polyurethane and the (B) polyester resin is 1.6 to. 2.0 It is a two-component paint composition.
  • the main agent of the present invention contains a polycarbonate-based polyurethane. Since polyurethane has urethane bonds, urea bonds, etc. inside, it is composed of hard segments strongly aggregated by strong hydrogen bonds and flexible soft segments composed of polyester or polyol portions.
  • the polycarbonate-based polyurethane means a polyurethane in which the polyol forming the soft segment is a polycarbonate polyol.
  • the polycarbonate polyol forming the soft segment can be obtained, for example, by reacting carbonates such as dialkyl carbonates with glycol, and has a polyol having two or more carbonate groups and hydroxyl groups in a molecular chain having a molecular weight of 500 to 3000.
  • carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropl carbonate, dibutyl carbonate, di-t-butyl carbonate, diamil carbonate, dihexyl carbonate, dicyclohexyl carbonate, and diheptyl carbonate. , Dioctyl carbonate, dicyclopropyl carbonate and the like.
  • glycols examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane.
  • the polycarbonate-based polyurethane exists as dispersed particles having an average particle size of 0.01 to 0.1 ⁇ m, preferably 0.015 to 0.07 ⁇ m, and more preferably 0.02 to 0.05 ⁇ m.
  • the average particle size can be measured by a dynamic light scattering method, a laser diffraction method, or the like.
  • Polycarbonate polyurethane preferably has a hydroxyl value of 100 to 300 mgKOH / g, more preferably 150 to 250 mgKOH / g, and even more preferably 180 to 220 mgKOH / g.
  • the hydroxyl value means a value corresponding to the mass (mg) of KOH required to neutralize 1 g of the sample.
  • a coating film having appropriate reactivity with the (C) hydrophilic polyisocyanate compound in the curing agent and having excellent lactic acid resistance and olein acid resistance can be formed.
  • Examples of commercially available polycarbonate-based polyurethanes include DPU2035ba (manufactured by Daicel Ornex), Nipponran 976 (manufactured by Tosoh), NeoRez R4000 (manufactured by DSM Coating Resins), and the like.
  • the content of the polycarbonate-based polyurethane in the main agent is, for example, 16 to 32% by mass, preferably 18 to 27% by mass, based on the total mass of the main agent.
  • a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
  • polyester resin is a resin obtained by polycondensing a polycarboxylic acid and a polyol.
  • Polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid, maleic acid.
  • Phthalic acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, octenyl succinic acid, dodecenyl succinic acid, etc. May use these anhydrides in place of the carboxylic acids described above.
  • the polyol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycol (for example, polyethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,2-butanediol.
  • the type of polyester resin can be appropriately determined according to the type of polycarbonate-based polyurethane used. By using a polyester resin having good compatibility with polycarbonate-based polyurethane, a high-gloss coating film can be formed.
  • the polyester resin has an average particle size of 0.01 ⁇ m or less, for example 0.001 to 0.01 ⁇ m. If the average particle size is within the above range, it is stably dissolved in water.
  • the average particle size can be measured by a dynamic light scattering method, a laser diffraction method, or the like.
  • the polyester resin preferably has a hydroxyl value of 100 to 200 mgKOH / g, more preferably 120 to 180 mgKOH / g.
  • a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
  • the polyester resin is preferably an amine-neutralized water-soluble polyester resin because it can form a coating film having excellent lactic acid resistance and olein acid resistance.
  • polyester resins examples include Resinol AN6617, AN6481, Steel 6306, and Setaqua BE270 (manufactured by Daicel Ornex).
  • the content of the polyester resin in the main agent is, for example, 5 to 15% by mass, preferably 6 to 13% by mass, based on the total mass of the main agent. When the content is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
  • the solid content mass ratio of the polycarbonate polyurethane (component A) and the polyester resin (component B) is preferably 8: 2 to 6: 4, and is 75: 25 to 65:35. Is more preferable.
  • the solid content mass ratio of (A): (B) is within the above range, the crosslink density and surface free energy of the coating film formed from the coating composition of the present invention can be within the desired range.
  • a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
  • the main agent of the present invention contains water.
  • the content of water in the main agent is, for example, 30 to 70% by mass, preferably 40 to 60% by mass, based on the total mass of the main agent.
  • a water-based paint having a reduced adverse effect on the environment can be obtained as compared with the conventional solvent-based paint.
  • the curing agent of the present invention contains a hydrophilic polyisocyanate compound.
  • the hydrophilic polyisocyanate contains a hydrophilic group having an affinity for water and a hydrophobic portion, and in water, the hydrophobic portions gather to form a micellar structure, so that the hydrophilic polyisocyanate can be easily and stably dispersed. Therefore, when mixed with the main agent, the reaction between isocyanate and water can be suppressed, and the cross-linking of the polycarbonate-based polyurethane and the polyester resin can be promoted.
  • hydrophilic group examples include an alkoxypolyalkyleneoxy group (for example, 2 to 50 carbon atoms), a carboxyl group, a sulfo group, and salts thereof (for example, a metal salt, an ammonium salt, and an amine salt).
  • an alkoxypolyalkyleneoxy group for example, 2 to 50 carbon atoms
  • carboxyl group for example, a carboxyl group
  • a sulfo group examples of the hydrophilic polyisocyanate
  • salts thereof for example, a metal salt, an ammonium salt, and an amine salt.
  • a polyisocyanate having a sulfo group forming an ammonium salt or the like can be preferably used.
  • an HMDI-based polyisocyanate is preferable.
  • the isocyanate group content of the hydrophilic polyisocyanate compound is preferably 10 to 30%, more preferably 15 to 25%, and even more preferably 19 to 22%.
  • the isocyanate group content represents the amount of isocyanate groups in the polyisocyanate compound as a mass fraction, and can be measured according to JIS K1603-1.
  • a coating film having excellent lactic acid resistance and olein acid resistance can be formed by reaction with the main agent.
  • the acid value of the hydrophilic polyisocyanate compound is preferably 0 to 30 mgKOH / g, more preferably 5 to 15 mgKOH / g. When the acid value is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
  • hydrophilic polyisocyanates for example, BASF2655, 3100, 302, 304, 305, XP2451 / 1, XP2487 / 1, XP2457, 401, XP2759 manufactured by Sumika Covestro Urethane, etc.
  • WB40, WT30, WT20, WL70, WR80, etc. and BASF's Basonat HW1000, HW2000, etc.
  • the coating composition of the present invention is a two-component coating composition containing a main agent and a curing agent.
  • the molar ratio NCO / OH is 1.6 to 2.0, preferably 1.7 to 1.9, and more preferably 1.8.
  • the crosslink density of the coating film formed by using the coating composition of the present invention can be within a desired range, and excellent lactic acid resistance and olein acid resistance can be obtained. Is given.
  • the molar ratio NCO / OH is the amount of NCO calculated from the hydroxyl values of (A) polycarbonate polyurethane and (B) polyester resin and the isocyanate group content of (C) hydrophilic polyisocyanate compound. Can be derived as the molar ratio of.
  • the coating composition of the present invention may contain a pigment.
  • the pigment include a coloring pigment, an extender pigment, a metal pigment and the like, and the pigment can be appropriately selected and used according to the coloring and gloss of the coating film, the coating workability, the strength of the coating film, the physical properties and the like.
  • Known materials can be used as the coloring pigment, and examples thereof include inorganic pigments such as titanium oxide and carbon black, and organic pigments such as phthalocyanine pigments and azo pigments.
  • known materials can be used as the extender pigment, and examples thereof include talc, mica, barium sulfate, clay, and calcium carbonate.
  • metal pigments include bright pigments or scaly pigments such as aluminum powder pigments, nickel powder pigments, gold powders, silver powders, bronze powders, copper powders, stainless powder pigments, mica (mica) pigments, graphite pigments, glass flake pigments, and the like.
  • bright pigments or scaly pigments such as aluminum powder pigments, nickel powder pigments, gold powders, silver powders, bronze powders, copper powders, stainless powder pigments, mica (mica) pigments, graphite pigments, glass flake pigments, and the like.
  • examples thereof include metal-coated glass powder, metal-coated mica powder, metal-coated plastic powder, and scaly iron oxide pigments.
  • the pigment can be blended in either the main agent or the curing agent, but it is preferably blended in the main agent.
  • the coating composition of the present invention contains additives commonly used in the coating industry, such as solvents, pH adjusters, surface adjusters, wetting agents, dispersants, emulsifiers, and additives.
  • Absorbents, antistatic agents, conductivity-imparting agents and the like can be appropriately blended according to the purpose.
  • silica particles into a coating composition a coating film having a matte feeling can be formed.
  • These optional components may be blended in either the main agent or the curing agent, or may be blended in both.
  • the two-component coating composition of the present invention can be prepared according to a conventional method.
  • each raw material may be uniformly mixed to prepare a main agent and a curing agent separately.
  • a water-based coating composition is prepared by mixing a main agent and a curing agent immediately before coating.
  • the coating method using the two-component coating composition of the present invention includes a step of mixing a main agent and a curing agent to obtain an aqueous coating composition, a step of applying the aqueous coating composition to the surface of a base material, and a step of applying the applied aqueous coating.
  • the step of drying the coating composition to form a coating film is included.
  • Conventionally known mixing means can be used for mixing the main agent and the curing agent without particular limitation.
  • the mixing ratio of the main agent and the curing agent can be appropriately adjusted by an amount such that the molar ratio NCO / OH in the aqueous coating composition immediately after mixing is 1.6 to 2.0.
  • the method for applying the water-based coating composition is not particularly limited, and known coating methods such as dipping method, spin coating method, flow coating method, roll coating method, spray coating method, blade coating method and air knife coating method are used. And so on. When applying the aqueous coating composition, it may be diluted with water to adjust the viscosity.
  • the coating amount of the water-based coating composition can be changed depending on the type and application of the base material, but is usually 54 to 81 g / m 2 , preferably 64 to 75 g / m 2.
  • the film thickness of the coating film formed on the surface of the base material depends on the coating amount of the aqueous coating composition, but is preferably 25 to 45 ⁇ m, for example, 30 to 40 ⁇ m. When the film thickness is within the above range, a coating film having sufficient lactic acid resistance and olein acid resistance can be obtained without requiring an excessive curing time.
  • the drying means is not particularly limited, and for example, it may be dried by heating, or it may be naturally dried at room temperature (for example, about 25 ° C.). It is preferable to combine both heating and natural drying. For example, it is preferably dried at 70 to 90 ° C., preferably 85 ° C. to 95 ° C. for 20 to 40 minutes, preferably 25 to 35 minutes, and then further dried at room temperature for 48 hours or more, preferably 60 to 80 hours. .. Such drying conditions are sufficient to form a coating film having the intended performance.
  • the coating film formed is, for example, a crosslink of 1.4 ⁇ 10 -3 to 1.7 ⁇ 10 -3 mol / mL, preferably 1.5 ⁇ 10 -3 to 1.7 ⁇ 10 -3 mol / mL.
  • the crosslink density can be determined based on the flat region storage elastic modulus measured under predetermined conditions using RSA-G2 (manufactured by TA instruments) and its absolute temperature, based on the following formula.
  • n E'/ 3RT n: Crosslink density (mol / mL) (1 / n: Molecular weight between crosslinks) R: Gas constant (8.31 ⁇ 106 Pa ⁇ cc / mol ⁇ K) T: Absolute temperature (K) of flat area storage elastic modulus E': Flat area storage modulus (Pa)
  • the coating film preferably has a surface free energy calculated from the Owns-Wendt equation of 50 mN / m or more, for example, 60 to 80 mN / m.
  • the Owns-Wend formula is one of the theoretical formulas of the surface free energy shown below, and the unknown surface free energy ( ⁇ d S + ⁇ p S ) of a solid is used as two kinds of liquids whose surface free energy is known.
  • the coating film corresponds to a solid in which the surface free energy in the formula is unknown, and the two liquids for measuring the contact angle correspond to liquids in which the surface free energy in the formula is known.
  • the base material to which the water-based coating composition is applied is not particularly limited, and various types and shapes can be selected depending on the use of the base material.
  • the base material include olefin-based polymers such as PPE (polyphenylene ether) resin, polystyrene-based resin, polypropylene and polyethylene; polycarbonate resin; acrylic resin such as polymethylmethacrylate and plastic base material such as ABS resin. ..
  • the present invention also relates to a coating material containing a base material and a coating film on the surface of the base material, and the coating film is formed by coating the above-mentioned water-based coating composition of the present invention.
  • the coating composition of the present invention can be applied to various substrates such as various inorganic substances, metals, woods, and plastics. Since the coating material of the present invention is excellent in lactic acid resistance and olein acid resistance, it is a plastic molded product that comes into contact with human skin or hands for a long time, specifically, interior and exterior members of automobiles and motorcycles, audio equipment. It is particularly useful for parts for home appliances such as video and television, and parts for office equipment such as mobile phones, printers, and personal computers.
  • ⁇ Paint preparation> The raw materials of the main agent were mixed according to the formulations shown in Table 1 and stirred with a disper for 10 minutes to prepare the main agents of Examples 1 to 3 and Comparative Examples 1 to 5.
  • the polycarbonate-based polyurethane was present as dispersed particles having an average particle size of 30 nm, and the polyester resin was dissolved in water.
  • each curing agent was added to the prepared main agent according to the formulation shown in Table 1, and the mixture was further stirred with a disper for 5 minutes to prepare the aqueous coating compositions of Examples 1 to 3 and Comparative Examples 1 to 5, respectively.
  • Each water-based coating composition prepared above is diluted with deionized water to a viscosity suitable for spray coating, and then coated on an ABS-PC resin plate by air spray coating so that the thickness of the dry coating film is 30 ⁇ 5 ⁇ m. Then, it was dried at 80 ° C. for 30 minutes, and further allowed to stand at room temperature for 72 hours to obtain each test piece.
  • ⁇ Appearance evaluation> The presence or absence of coating film abnormalities such as bumps, cracks, wrinkles, repellents, peelings, and blisters was visually confirmed.
  • ⁇ Adhesiveness evaluation> According to JIS K 5600-5-6 (cross-cut method), make a notch of 2 mm square grid 10 x 10 squares in the coating film after painting, attach cellophane tape to the grid, and peel it off rapidly. After that, the number of Goban-grained coating films remaining on the coated surface was evaluated. ⁇ : No peeling coating film ⁇ : Part of the coating film is missing along the notch ⁇ : The coating film is peeled off
  • the coating composition of the present invention is particularly useful as a coating material for interior and exterior members of automobiles and motorcycles, members for home appliances such as audio, video and television, and members for office equipment such as mobile phones, printers and personal computers. ..

Abstract

Provided is a water-based coating material composition that can form a coating film having excellent lactic acid resistance and oleic acid resistance.　This composition includes: a main agent containing a polycarbonate-based polyurethane, a polyester resin, and water; and a curing agent containing a hydrophilic polyisocyanate compound. The main agent and the curing agent are blended such that the molar ratio of hydroxyl groups (OH) in the main agent and isocyanate groups (NCO) in the curing agent falls within a specific range.

Description

２液型塗料組成物及び塗装物Two-component paint composition and paint
　本発明は、２液型塗料組成物並びにそれから得られる水性塗料組成物、塗膜及び塗装物に関する。 The present invention relates to a two-component coating composition and a water-based coating composition, a coating film and a coating material obtained from the two-component coating composition.
　プラスチック成形品は、可塑性を持つ高分子物質の成形体であり、携帯電話、家電製品、ＯＡ機器等に利用されており、該プラスチック成形品の表面は、装飾を施したり又は機能を付与したりするために塗装されている場合がある。そのため、プラスチックを塗装するための塗料（プラスチック用塗料）は、装飾を施す他、プラスチック成形品の用途に応じて、塗膜に耐摩耗性、耐変退色性、耐皮脂性、高光沢性、高耐候性、電気絶縁性等の機能を付与することが求められる場合がある。 A plastic molded product is a molded product of a polymer substance having plasticity, and is used for mobile phones, home appliances, OA equipment, etc., and the surface of the plastic molded product is decorated or given a function. May be painted to. Therefore, the paint for painting plastic (paint for plastic) not only decorates, but also has abrasion resistance, discoloration resistance, skin oil resistance, and high gloss resistance, depending on the application of the plastic molded product. It may be required to impart functions such as high weather resistance and electrical insulation.
　特に、人の肌や手が長時間接触するようなプラスチック成形品（例えば、携帯電話の外装部材や自動車内装部材）については、汗、ハンドクリーム、日焼け止め、サンオイル等の成分である乳酸に対する耐性（耐乳酸性）や、皮脂中に含まれる成分であるオレイン酸に対する耐性（耐オレイン酸性）に優れることが求められる。また、自動車内装部材については、高光沢感や艶消し感を求められる場合もある。 In particular, for plastic molded products that come into contact with human skin or hands for a long time (for example, mobile phone exterior members and automobile interior components), lactic acid, which is a component of sweat, hand cream, sunscreen, sun oil, etc. It is required to have excellent resistance (lactic acid resistance) and resistance to oleic acid (oleic acid resistance), which is a component contained in sebum. In addition, there are cases where a high glossy feeling and a matte feeling are required for automobile interior members.
　自動車内装用塗料としては、従来から、溶剤系ラッカー塗料や溶剤系２液硬化型ウレタン塗料が用いられている。一方、環境規制が厳しくなってきたことから、塗料業界では有機溶剤を使用した溶剤系塗料から水を使用した水性塗料への転換がなされつつある。しかしながら、水性塗料においては、十分な耐乳酸性や耐オレイン酸性を有する塗膜は得られなかった。 Conventionally, solvent-based lacquer paints and solvent-based two-component curable urethane paints have been used as paints for automobile interiors. On the other hand, as environmental regulations have become stricter, the paint industry is shifting from solvent-based paints that use organic solvents to water-based paints that use water. However, in the water-based paint, a coating film having sufficient lactic acid resistance and olein acid resistance could not be obtained.
　本発明の課題は、優れた耐乳酸性及び耐オレイン酸性を有する塗膜を形成できる水性塗料組成物を提供することである。 An object of the present invention is to provide an aqueous coating composition capable of forming a coating film having excellent lactic acid resistance and olein acid resistance.
　上記課題は、ポリカーボネート系ポリウレタン、ポリエステル樹脂及び水を含む主剤と、親水性ポリイソシアネート化合物を含む硬化剤とを、主剤中の水酸基（ＯＨ）と硬化剤中のイソシアネート基（ＮＣＯ）とのモル比が特定の範囲となるように配合することによって解決できることが見出された。すなわち、本発明は、下記〔１〕～〔１４〕に関するものである。 The above problem is the molar ratio of the hydroxyl group (OH) in the main agent and the isocyanate group (NCO) in the curing agent of the main agent containing polycarbonate polyurethane, polyester resin and water and the curing agent containing a hydrophilic polyisocyanate compound. It was found that this can be solved by blending so that is in a specific range. That is, the present invention relates to the following [1] to [14].
〔１〕主剤と硬化剤とを含む２液型塗料組成物であって、
　前記主剤が、（Ａ）ポリカーボネート系ポリウレタン、（Ｂ）ポリエステル樹脂、及び水を含み、前記（Ａ）ポリカーボネート系ポリウレタンが、０．０１～０．１μｍの平均粒子径を有し、前記（Ｂ）ポリエステル樹脂が、０．０１μｍ以下の平均粒子径を有し、
　前記硬化剤が、（Ｃ）親水性ポリイソシアネート化合物を含み、
　前記（Ｃ）親水性ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と、前記（Ａ）ポリカーボネート系ポリウレタン及び前記（Ｂ）ポリエステル樹脂中の水酸基（ＯＨ）のモル比ＮＣＯ／ＯＨが、１．６～２．０である、
２液型塗料組成物。
〔２〕前記（Ｂ）ポリエステル樹脂の水酸基価が、１００～２００ｍｇＫＯＨ／ｇである、前記〔１〕に記載の２液型塗料組成物。
〔３〕前記（Ｃ）親水性ポリイソシアネート化合物のイソシアネート基含有率が、１５～２５％である、前記〔１〕又は〔２〕に記載の２液型塗料組成物。
〔４〕前記（Ａ）ポリカーボネート系ポリウレタンと前記（Ｂ）ポリエステル樹脂の固形分質量比が、８：２～６：４である、前記〔１〕～〔３〕のいずれか１項に記載の２液型塗料組成物。
〔５〕前記主剤が、カーボンブラック、金属顔料及び有機顔料からなる群から選択される着色剤を更に含む、前記〔１〕～〔４〕のいずれか１項に記載の２液型塗料組成物。
〔６〕前記〔１〕～〔５〕のいずれか１項に記載の２液型塗料組成物の前記主剤と前記硬化剤とを配合してなる、水性塗料組成物。
〔７〕前記〔６〕に記載の水性塗料組成物を塗装して形成された塗膜。
〔８〕架橋密度が、１．４×１０-3～１．７×１０-3ｍｏｌ／ｍＬである、前記〔７〕に記載の塗膜。
〔９〕Ｏｗｅｎｓ－Ｗｅｎｄｔ式から算出される表面自由エネルギーが、５０ｍＮ／ｍ以上である、前記〔７〕又は〔８〕に記載の塗膜。
〔１０〕基材と、前記基材の表面上の前記〔７〕～〔９〕のいずれか１項に記載の塗膜とを含む、塗装物。
〔１１〕前記基材が、プラスチックである、前記〔１０〕に記載の塗装物。
〔１２〕基材の塗装方法であって、以下の工程、
　前記〔１〕～〔５〕のいずれか１項に記載の２液型塗料組成物の前記主剤と前記硬化剤とを混合して、水性塗料組成物を得る工程、
　前記水性塗料組成物を基材の表面に塗布する工程、
　前記塗布した水性塗料組成物を乾燥させて塗膜を形成する工程、
を含む、方法。
〔１３〕前記乾燥を、７０℃～９０℃で２０～４０分、続いて常温で４８時間以上行う、前記〔１２〕に記載の方法。
〔１４〕前記塗膜が、２５μｍ～４５μｍの厚さを有する、前記〔１２〕又は〔１３〕に記載の塗装方法。 [1] A two-component coating composition containing a main agent and a curing agent.
The main agent contains (A) polycarbonate-based polyurethane, (B) polyester resin, and water, and the (A) polycarbonate-based polyurethane has an average particle size of 0.01 to 0.1 μm, and the (B) The polyester resin has an average particle size of 0.01 μm or less and has an average particle size of 0.01 μm or less.
The curing agent contains (C) a hydrophilic polyisocyanate compound.
The molar ratio NCO / OH of the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound and the hydroxyl group (OH) in the (A) polycarbonate-based polyurethane and the (B) polyester resin is 1.6 to. 2.0
Two-component paint composition.
[2] The two-component coating composition according to the above [1], wherein the polyester resin (B) has a hydroxyl value of 100 to 200 mgKOH / g.
[3] The two-component coating composition according to the above [1] or [2], wherein the (C) hydrophilic polyisocyanate compound has an isocyanate group content of 15 to 25%.
[4] The item according to any one of the above [1] to [3], wherein the solid content mass ratio of the (A) polycarbonate-based polyurethane and the (B) polyester resin is 8: 2 to 6: 4. Two-component paint composition.
[5] The two-component coating composition according to any one of [1] to [4] above, wherein the main agent further contains a colorant selected from the group consisting of carbon black, metal pigments and organic pigments. ..
[6] A water-based coating composition comprising the main agent and the curing agent of the two-component coating composition according to any one of the above [1] to [5].
[7] A coating film formed by coating the water-based coating composition according to the above [6].
[8] The coating film according to the above [7], wherein the crosslink density is 1.4 × 10 -3 to 1.7 × 10 -3 mol / mL.
[9] The coating film according to the above [7] or [8], wherein the surface free energy calculated from the Owns-Wendt equation is 50 mN / m or more.
[10] A coating material comprising the base material and the coating film according to any one of the above [7] to [9] on the surface of the base material.
[11] The coating material according to the above [10], wherein the base material is a plastic.
[12] A method for coating a base material, which comprises the following steps.
A step of mixing the main agent and the curing agent of the two-component coating composition according to any one of [1] to [5] to obtain an aqueous coating composition.
The step of applying the water-based coating composition to the surface of the base material,
The step of drying the applied aqueous coating composition to form a coating film,
Including methods.
[13] The method according to [12] above, wherein the drying is carried out at 70 ° C. to 90 ° C. for 20 to 40 minutes, and then at room temperature for 48 hours or more.
[14] The coating method according to the above [12] or [13], wherein the coating film has a thickness of 25 μm to 45 μm.
　本発明によって、優れた耐乳酸性及び耐オレイン酸性を有する塗膜を形成できる水性塗料組成物を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an aqueous coating composition capable of forming a coating film having excellent lactic acid resistance and olein acid resistance.
　本発明は、主剤と硬化剤とを含む２液型塗料組成物であって、
　前記主剤が、（Ａ）ポリカーボネート系ポリウレタン、（Ｂ）ポリエステル樹脂、及び水を含み、前記（Ａ）ポリカーボネート系ポリウレタンが、０．０１～０．１μｍの平均粒子径を有し、前記（Ｂ）ポリエステル樹脂が、０．０１μｍ以下の平均粒子径を有し、
　前記硬化剤が、（Ｃ）親水性ポリイソシアネート化合物を含み、
　前記（Ｃ）親水性ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と、前記（Ａ）ポリカーボネート系ポリウレタン及び前記（Ｂ）ポリエステル樹脂中の水酸基（ＯＨ）のモル比ＮＣＯ／ＯＨが、１．６～２．０である、
２液型塗料組成物である。 The present invention is a two-component coating composition containing a main agent and a curing agent.
The main agent contains (A) polycarbonate-based polyurethane, (B) polyester resin, and water, and the (A) polycarbonate-based polyurethane has an average particle size of 0.01 to 0.1 μm, and the (B) The polyester resin has an average particle size of 0.01 μm or less and has an average particle size of 0.01 μm or less.
The curing agent contains (C) a hydrophilic polyisocyanate compound.
The molar ratio NCO / OH of the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound and the hydroxyl group (OH) in the (A) polycarbonate-based polyurethane and the (B) polyester resin is 1.6 to. 2.0
It is a two-component paint composition.
（Ａ）ポリカーボネート系ポリウレタン
　本発明の主剤は、ポリカーボネート系ポリウレタンを含む。ポリウレタンは、その内部にウレタン結合、ウレア結合等を有することから、強固な水素結合により強く凝集したハードセグメントと、ポリエステル又はポリオール部分からなるフレキシブルなソフトセグメントから構成される。ポリカーボネート系ポリウレタンとは、ソフトセグメントを形成するポリオールがポリカーボネートポリオールであるポリウレタンを意味する。 (A) Polycarbonate-based polyurethane The main agent of the present invention contains a polycarbonate-based polyurethane. Since polyurethane has urethane bonds, urea bonds, etc. inside, it is composed of hard segments strongly aggregated by strong hydrogen bonds and flexible soft segments composed of polyester or polyol portions. The polycarbonate-based polyurethane means a polyurethane in which the polyol forming the soft segment is a polycarbonate polyol.
　ソフトセグメントを形成するポリカーボネートポリオールは、例えば、ジアルキルカーボネート類等のカーボネート類とグリコールとの反応によって得ることができ、分子量５００～３０００の分子鎖中にカーボネート基と水酸基をそれぞれ２つ以上有するポリオールをいう。カーボネート類としては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジ－ｎ－プロピルカーボネート、ジイソプロプルカーボネート、ジブチルカーボネート、ジ－ｔ－ブチルカーボネート、ジアミルカーボネート、ジへキシルカーボネート、ジシクロヘキシルカーボネート、ジヘプチルカーボネート、ジオクチルカーボネート、ジシクロプロピルカーボネート等が挙げられる。グリコールとしては、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、２－エチル－１，６－ヘキサンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、１，３－シクロヘキサンジオール、１，４－シクロヘキサンジオール、２，２´－ビス－（４－ヒドロキシシクロヘキシル）－プロパン、ｐ－キシレンジオール、ｐ－テトラクロロキシレンジオール、１，４－ジメチロールシクロヘキサン、（３（４），８（９）－ビス－（ヒドロキシメチル）－トリシクロデカンジメチロール、ビス－ヒドロキシメチルテトラヒドロフラン、ジ（２－ヒドロキシエチル）ジメチルヒダントイン、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられる。 The polycarbonate polyol forming the soft segment can be obtained, for example, by reacting carbonates such as dialkyl carbonates with glycol, and has a polyol having two or more carbonate groups and hydroxyl groups in a molecular chain having a molecular weight of 500 to 3000. Say. Examples of carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropl carbonate, dibutyl carbonate, di-t-butyl carbonate, diamil carbonate, dihexyl carbonate, dicyclohexyl carbonate, and diheptyl carbonate. , Dioctyl carbonate, dicyclopropyl carbonate and the like. Examples of glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane. Diol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2'-bis- ( 4-Hydroxycyclohexyl) -propane, p-xylenediol, p-tetrachloroxylenediol, 1,4-dimethylolcyclohexane, (3 (4), 8 (9) -bis- (hydroxymethyl) -tricyclodecandi Examples thereof include methylol, bis-hydroxymethyl tetrahydrofuran, di (2-hydroxyethyl) dimethyl hydantin, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
　主剤中、ポリカーボネート系ポリウレタンは、０．０１～０．１μｍ、好ましくは０．０１５～０．０７μｍ、より好ましくは０．０２～０．０５μｍの平均粒子径を有する分散粒子として存在する。平均粒子径が上記範囲内であれば、水中での分散状態が安定している。平均粒子径は、動的光散乱法、レーザー回折法などによって測定することができる。 In the main agent, the polycarbonate-based polyurethane exists as dispersed particles having an average particle size of 0.01 to 0.1 μm, preferably 0.015 to 0.07 μm, and more preferably 0.02 to 0.05 μm. When the average particle size is within the above range, the dispersed state in water is stable. The average particle size can be measured by a dynamic light scattering method, a laser diffraction method, or the like.
　ポリカーボネート系ポリウレタンは、好ましくは１００～３００ｍｇＫＯＨ／ｇ、より好ましくは１５０～２５０ｍｇＫＯＨ／ｇ、更により好ましくは１８０～２２０ｍｇＫＯＨ／ｇの水酸基価を有する。水酸基価は、試料１ｇを中和するのに必要となるＫＯＨの質量（ｍｇ）に相当する値を意味する。水酸基価が上記範囲内であれば、硬化剤中の（Ｃ）親水性ポリイソシアネート化合物と適度な反応性を有し、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成できる。 Polycarbonate polyurethane preferably has a hydroxyl value of 100 to 300 mgKOH / g, more preferably 150 to 250 mgKOH / g, and even more preferably 180 to 220 mgKOH / g. The hydroxyl value means a value corresponding to the mass (mg) of KOH required to neutralize 1 g of the sample. When the hydroxyl value is within the above range, a coating film having appropriate reactivity with the (C) hydrophilic polyisocyanate compound in the curing agent and having excellent lactic acid resistance and olein acid resistance can be formed.
　市販のポリカーボネート系ポリウレタンとしては、例えばＤＰＵ２０３５ｂａ（ダイセル・オルネクス社製）、ニッポラン９７６（東ソー社製）、ＮｅｏＲｅｚ　Ｒ４０００（ＤＳＭ　Ｃｏａｔｉｎｇ　Ｒｅｓｉｎｓ社製）等がある。 Examples of commercially available polycarbonate-based polyurethanes include DPU2035ba (manufactured by Daicel Ornex), Nipponran 976 (manufactured by Tosoh), NeoRez R4000 (manufactured by DSM Coating Resins), and the like.
　主剤におけるポリカーボネート系ポリウレタンの含有量は、主剤の総質量に基づき、例えば、１６～３２質量％であり、好ましくは１８～２７質量％である。含有量が上記範囲内であれば、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成することができる。 The content of the polycarbonate-based polyurethane in the main agent is, for example, 16 to 32% by mass, preferably 18 to 27% by mass, based on the total mass of the main agent. When the content is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
（Ｂ）ポリエステル樹脂
　ポリエステル樹脂は、ポリカルボン酸とポリオールとを重縮合させることで得られる樹脂である。ポリカルボン酸としては、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、シクロヘキサンジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、グルタル酸、クロレンド酸、テトラクロロフタル酸、マレイン酸、フマル酸、イタコン酸、マロン酸、スベリン酸、２－メチルコハク酸、３，３－ジエチルグルタル酸、２，２－ジメチルコハク酸、オクテニルコハク酸、ドデセニルコハク酸等を挙げることができ、存在する場合には前記のカルボン酸の代わりにこれらの無水物を使用してもよい。また、ポリオールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリアルキレングリコール（例えば、ポリエチレングリコール）、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、ネオペンチルグリコールヒドロキシピルビン酸塩、ジメチロールシクロヘキサン、トリメチロールプロパン、グリセロール、エリスリトール、ペンタエリスリトール、トリメチロールベンゼン、トリスヒドロキシエチルイソシアヌレート等を挙げることができる。ポリエステル樹脂の種類は、使用するポリカーボネート系ポリウレタンの種類に応じて適宜決定できる。ポリカーボネート系ポリウレタンとの相溶性の良いポリエステル樹脂を用いることで、高光沢の塗膜を形成することができる。 (B) Polyester resin The polyester resin is a resin obtained by polycondensing a polycarboxylic acid and a polyol. Polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid, maleic acid. , Phthalic acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, octenyl succinic acid, dodecenyl succinic acid, etc. May use these anhydrides in place of the carboxylic acids described above. Examples of the polyol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycol (for example, polyethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,2-butanediol. Diol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol hydroxypyrvate, dimethylolcyclohexane, trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene, trishydroxyethyl Isocyanurate and the like can be mentioned. The type of polyester resin can be appropriately determined according to the type of polycarbonate-based polyurethane used. By using a polyester resin having good compatibility with polycarbonate-based polyurethane, a high-gloss coating film can be formed.
　主剤において、ポリエステル樹脂は、０．０１μｍ以下、例えば０．００１～０．０１μｍの平均粒子径を有する。平均粒子径が上記範囲内であれば、水中に安定して溶存している。平均粒子径は、動的光散乱法、レーザー回折法などによって測定することができる。 In the main agent, the polyester resin has an average particle size of 0.01 μm or less, for example 0.001 to 0.01 μm. If the average particle size is within the above range, it is stably dissolved in water. The average particle size can be measured by a dynamic light scattering method, a laser diffraction method, or the like.
　ポリエステル樹脂は、好ましくは１００～２００ｍｇＫＯＨ／ｇ、より好ましくは１２０～１８０ｍｇＫＯＨ／ｇの水酸基価を有する。水酸基価が上記範囲内であれば、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成することができる。 The polyester resin preferably has a hydroxyl value of 100 to 200 mgKOH / g, more preferably 120 to 180 mgKOH / g. When the hydroxyl value is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
　ポリエステル樹脂は、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成できることから、アミンで中和された水溶性のポリエステル樹脂であることが好ましい。 The polyester resin is preferably an amine-neutralized water-soluble polyester resin because it can form a coating film having excellent lactic acid resistance and olein acid resistance.
　市販のポリエステル樹脂としては、例えばＲｅｓｙｄｒｏｌ　ＡＮ６６１７、ＡＮ６４８１、Ｓｅｔａｌ　６３０６、Ｓｅｔａｑｕａ　ＢＥ２７０（ダイセル・オルネクス社製）等がある。 Examples of commercially available polyester resins include Resinol AN6617, AN6481, Steel 6306, and Setaqua BE270 (manufactured by Daicel Ornex).
　主剤におけるポリエステル樹脂の含有量は、主剤の総質量に基づき、例えば、５～１５質量％であり、好ましくは６～１３質量％である。含有量が上記範囲内であれば、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成することができる。 The content of the polyester resin in the main agent is, for example, 5 to 15% by mass, preferably 6 to 13% by mass, based on the total mass of the main agent. When the content is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
　本発明の主剤において、ポリカーボネート系ポリウレタン（Ａ成分）とポリエステル樹脂（Ｂ成分）の固形分質量比は、８：２～６：４であることが好ましく、７５：２５～６５：３５であることがより好ましい。（Ａ）：（Ｂ）の固形分質量比が上記範囲内であれば、本発明の塗料組成物から形成される塗膜の架橋密度及び表面自由エネルギーを所望の範囲内にすることができ、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成することができる。 In the main agent of the present invention, the solid content mass ratio of the polycarbonate polyurethane (component A) and the polyester resin (component B) is preferably 8: 2 to 6: 4, and is 75: 25 to 65:35. Is more preferable. When the solid content mass ratio of (A): (B) is within the above range, the crosslink density and surface free energy of the coating film formed from the coating composition of the present invention can be within the desired range. A coating film having excellent lactic acid resistance and olein acid resistance can be formed.
　本発明の主剤は、水を含む。主剤における水の含有量は、主剤の総質量に基づき、例えば、３０～７０質量％であり、好ましくは４０～６０質量％である。水の含有量が上記範囲内であれば、従来の溶剤系塗料よりも環境への悪影響が低減された水性塗料を得ることができる。 The main agent of the present invention contains water. The content of water in the main agent is, for example, 30 to 70% by mass, preferably 40 to 60% by mass, based on the total mass of the main agent. When the water content is within the above range, a water-based paint having a reduced adverse effect on the environment can be obtained as compared with the conventional solvent-based paint.
　（Ｃ）親水性ポリイソシアネート化合物
　本発明の硬化剤は、親水性ポリイソシアネート化合物を含む。親水性ポリイソシアネートは、水との親和性を有する親水性基と疎水性部分を含み、水中では、疎水性部分が集まってミセル構造をとることで、容易かつ安定して分散することができる。そのため、主剤と混合した場合には、イソシアネートと水との反応を抑制して、ポリカーボネート系ポリウレタン及びポリエステル樹脂の架橋を促進することができる。親水性基としては、例えば、アルコキシポリアルキレンオキシ基（炭素数が例えば２～５０）、カルボキシル基、スルホ基、及びこれらの塩（例えば、金属塩、アンモニウム塩、アミン塩）等が挙げられる。親水性ポリイソシアネートとしては、アンモニウム塩を形成するスルホ基を有するポリイソシアネート等を好適に用いることができる。また、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成できることから、ＨＭＤＩ系のポリイソシアネートであることが好ましい。 (C) Hydrophilic Polyisocyanate Compound The curing agent of the present invention contains a hydrophilic polyisocyanate compound. The hydrophilic polyisocyanate contains a hydrophilic group having an affinity for water and a hydrophobic portion, and in water, the hydrophobic portions gather to form a micellar structure, so that the hydrophilic polyisocyanate can be easily and stably dispersed. Therefore, when mixed with the main agent, the reaction between isocyanate and water can be suppressed, and the cross-linking of the polycarbonate-based polyurethane and the polyester resin can be promoted. Examples of the hydrophilic group include an alkoxypolyalkyleneoxy group (for example, 2 to 50 carbon atoms), a carboxyl group, a sulfo group, and salts thereof (for example, a metal salt, an ammonium salt, and an amine salt). As the hydrophilic polyisocyanate, a polyisocyanate having a sulfo group forming an ammonium salt or the like can be preferably used. Further, since a coating film having excellent lactic acid resistance and olein acid resistance can be formed, an HMDI-based polyisocyanate is preferable.
　親水性ポリイソシアネート化合物のイソシアネート基含有率は、好ましくは１０～３０％、より好ましくは１５～２５％、更により好ましくは１９～２２％である。ここで、イソシアネート基含有率とは、ポリイソシアネート化合物中のイソシアネート基量を質量分率で表したものであり、ＪＩＳ　Ｋ１６０３－１に従って測定することができる。イソシアネート基含有率が上記範囲内であれば、主剤との反応により、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成できる。 The isocyanate group content of the hydrophilic polyisocyanate compound is preferably 10 to 30%, more preferably 15 to 25%, and even more preferably 19 to 22%. Here, the isocyanate group content represents the amount of isocyanate groups in the polyisocyanate compound as a mass fraction, and can be measured according to JIS K1603-1. When the isocyanate group content is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed by reaction with the main agent.
　親水性ポリイソシアネート化合物の酸価は、好ましくは０～３０ｍｇＫＯＨ／ｇであり、より好ましくは５～１５ｍｇＫＯＨ／ｇである。酸価が上記範囲内であれば、耐乳酸性及び耐オレイン酸性に優れた塗膜を形成できる。 The acid value of the hydrophilic polyisocyanate compound is preferably 0 to 30 mgKOH / g, more preferably 5 to 15 mgKOH / g. When the acid value is within the above range, a coating film having excellent lactic acid resistance and olein acid resistance can be formed.
　市販の親水性ポリイソシアネートとしては、例えば、住化コベストロウレタン社製のバイヒジュールＸＰ２６５５、３１００、３０２、３０４、３０５、ＸＰ２４５１/１、ＸＰ２４８７/１、ＸＰ２４５７、４０１、ＸＰ２７５９等、旭化成社製のデュラネートＷＢ４０、ＷＴ３０、ＷＴ２０、ＷＬ７０、ＷＲ８０等、ＢＡＳＦ社製のＢａｓｏｎａｔ　ＨＷ１０００、ＨＷ２０００等がある。 As commercially available hydrophilic polyisocyanates, for example, BASF2655, 3100, 302, 304, 305, XP2451 / 1, XP2487 / 1, XP2457, 401, XP2759 manufactured by Sumika Covestro Urethane, etc. There are WB40, WT30, WT20, WL70, WR80, etc., and BASF's Basonat HW1000, HW2000, etc.
　本発明の塗料組成物は、主剤と硬化剤とを含む２液型塗料組成物である。本発明の２液型塗料組成物において、硬化剤における（Ｃ）親水性ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と、主剤における（Ａ）ポリカーボネート系ポリウレタン及び（Ｂ）ポリエステル樹脂中の水酸基（ＯＨ）のモル比ＮＣＯ／ＯＨは、１．６～２．０であり、好ましくは１．７～１．９であり、より好ましくは１．８である。ＮＣＯ／ＯＨ比を上記範囲内とすることによって、本発明の塗料組成物を用いて形成される塗膜の架橋密度を所望の範囲内にすることができ、優れた耐乳酸性及び耐オレイン酸性が付与される。上記モル比ＮＣＯ／ＯＨは、（Ａ）ポリカーボネート系ポリウレタン及び（Ｂ）ポリエステル樹脂の水酸基価から算出されるＯＨ量と、（Ｃ）親水性ポリイソシアネート化合物のイソシアネート基含有率より算出されるＮＣＯ量のモル比率として導くことができる。 The coating composition of the present invention is a two-component coating composition containing a main agent and a curing agent. In the two-component coating composition of the present invention, the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound in the curing agent and the hydroxyl group (OH) in the (A) polycarbonate polyurethane and (B) polyester resin in the main agent. ), The molar ratio NCO / OH is 1.6 to 2.0, preferably 1.7 to 1.9, and more preferably 1.8. By setting the NCO / OH ratio within the above range, the crosslink density of the coating film formed by using the coating composition of the present invention can be within a desired range, and excellent lactic acid resistance and olein acid resistance can be obtained. Is given. The molar ratio NCO / OH is the amount of NCO calculated from the hydroxyl values of (A) polycarbonate polyurethane and (B) polyester resin and the isocyanate group content of (C) hydrophilic polyisocyanate compound. Can be derived as the molar ratio of.
　本発明の塗料組成物は、顔料を含んでもよい。顔料としては、着色顔料、体質顔料及び金属顔料等が挙げられ、塗膜の着色やツヤ、塗装作業性、塗膜の強度、物性等に応じて適宜選択して使用できる。着色顔料は、公知の材料が使用でき、例えば、酸化チタン及びカーボンブラック等の無機顔料やフタロシアニン系顔料及びアゾ系顔料等の有機顔料が挙げられる。また、体質顔料も、公知の材料が使用でき、例えば、タルク、マイカ、硫酸バリウム、クレー、炭酸カルシウム等が挙げられる。金属顔料としては、光輝顔料又は鱗片状顔料、例えば、アルミニウム粉顔料、ニッケル粉顔料、金粉、銀粉、ブロンズ粉、銅粉、ステンレス粉顔料、マイカ（雲母）顔料、グラファイト顔料、ガラスフレーク顔料や、金属コーティングした硝子粉、金属コーティングしたマイカ粉、金属コーティングしたプラスチック粉、及び鱗片状酸化鉄顔料等が挙げられる。顔料は主剤と硬化剤のいずれにも配合できるが、主剤に配合するのが好ましい。 The coating composition of the present invention may contain a pigment. Examples of the pigment include a coloring pigment, an extender pigment, a metal pigment and the like, and the pigment can be appropriately selected and used according to the coloring and gloss of the coating film, the coating workability, the strength of the coating film, the physical properties and the like. Known materials can be used as the coloring pigment, and examples thereof include inorganic pigments such as titanium oxide and carbon black, and organic pigments such as phthalocyanine pigments and azo pigments. Also, known materials can be used as the extender pigment, and examples thereof include talc, mica, barium sulfate, clay, and calcium carbonate. Examples of metal pigments include bright pigments or scaly pigments such as aluminum powder pigments, nickel powder pigments, gold powders, silver powders, bronze powders, copper powders, stainless powder pigments, mica (mica) pigments, graphite pigments, glass flake pigments, and the like. Examples thereof include metal-coated glass powder, metal-coated mica powder, metal-coated plastic powder, and scaly iron oxide pigments. The pigment can be blended in either the main agent or the curing agent, but it is preferably blended in the main agent.
　本発明の塗料組成物は、上記Ａ～Ｃ成分や顔料の他に、塗料業界で通常使用される添加剤、例えば、溶剤、ｐＨ調整剤、表面調整剤、湿潤剤、分散剤、乳化剤、増粘剤、沈降防止剤、皮張り防止剤、たれ防止剤、消泡剤、色分かれ防止剤、レベリング剤、乾燥剤、可塑剤、防カビ剤、抗菌剤、殺虫剤、光安定化剤、紫外線吸収剤、帯電防止剤及び導電性付与剤等を目的に応じて適宜配合することができる。特に、シリカ粒子を塗料組成物に配合することで、艶消し感のある塗膜を形成することができる。これらの任意成分は、主剤及び硬化剤のいずれに配合してもよく、両方に配合してもよい。 In addition to the above-mentioned components A to C and pigments, the coating composition of the present invention contains additives commonly used in the coating industry, such as solvents, pH adjusters, surface adjusters, wetting agents, dispersants, emulsifiers, and additives. Adhesives, anti-settling agents, anti-skin agents, anti-dripping agents, anti-foaming agents, anti-color separation agents, leveling agents, desiccants, plasticizers, antifungal agents, antibacterial agents, insecticides, light stabilizers, ultraviolet rays Absorbents, antistatic agents, conductivity-imparting agents and the like can be appropriately blended according to the purpose. In particular, by blending silica particles into a coating composition, a coating film having a matte feeling can be formed. These optional components may be blended in either the main agent or the curing agent, or may be blended in both.
　本発明の２液型塗料組成物は、常法に従って調製が可能である。例えば、各原料を均一に混合して主剤及び硬化剤を別個に調製してもよい。塗装直前に主剤と硬化剤を混合することにより、水性塗料組成物が調製される。 The two-component coating composition of the present invention can be prepared according to a conventional method. For example, each raw material may be uniformly mixed to prepare a main agent and a curing agent separately. A water-based coating composition is prepared by mixing a main agent and a curing agent immediately before coating.
　本発明の２液型塗料組成物を用いる塗装方法は、主剤と硬化剤とを混合して、水性塗料組成物を得る工程、水性塗料組成物を基材の表面に塗布する工程、塗布した水性塗料組成物を乾燥させて塗膜を形成する工程を含む。 The coating method using the two-component coating composition of the present invention includes a step of mixing a main agent and a curing agent to obtain an aqueous coating composition, a step of applying the aqueous coating composition to the surface of a base material, and a step of applying the applied aqueous coating. The step of drying the coating composition to form a coating film is included.
　主剤と硬化剤の混合には、従来公知の混合手段を特に制限なく用いることができる。主剤と硬化剤の混合比は、混合直後の水性塗料組成物における上記モル比ＮＣＯ／ＯＨが１．６～２．０となる量で適宜調節できる。水性塗料組成物を塗布する方法としては、特に制限されず、公知の塗布方法、例えば、ディッピング法、スピンコート法、フローコート法、ロールコート法、スプレーコート法、ブレードコート法及びエアーナイフコート法等が挙げられる。水性塗料組成物を塗布する際、粘度を調節するために水で希釈してもよい。水性塗料組成物の塗布量は、基材の種類や用途に応じて変えることができるが、通常、５４～８１ｇ／ｍ2であり、６４～７５ｇ／ｍ2であることが好ましい。なお、基材表面に形成される塗膜の膜厚は、水性塗料組成物の塗布量に依存するが、２５～４５μｍ、例えば３０～４０μｍであることが好ましい。膜厚が上記範囲内であれば、過度の硬化時間を要することなく十分な耐乳酸性及び耐オレイン酸性を有する塗膜が得られる。 Conventionally known mixing means can be used for mixing the main agent and the curing agent without particular limitation. The mixing ratio of the main agent and the curing agent can be appropriately adjusted by an amount such that the molar ratio NCO / OH in the aqueous coating composition immediately after mixing is 1.6 to 2.0. The method for applying the water-based coating composition is not particularly limited, and known coating methods such as dipping method, spin coating method, flow coating method, roll coating method, spray coating method, blade coating method and air knife coating method are used. And so on. When applying the aqueous coating composition, it may be diluted with water to adjust the viscosity. The coating amount of the water-based coating composition can be changed depending on the type and application of the base material, but is usually 54 to 81 g / m 2 , preferably 64 to 75 g / m 2. The film thickness of the coating film formed on the surface of the base material depends on the coating amount of the aqueous coating composition, but is preferably 25 to 45 μm, for example, 30 to 40 μm. When the film thickness is within the above range, a coating film having sufficient lactic acid resistance and olein acid resistance can be obtained without requiring an excessive curing time.
　乾燥手段には特に制限はなく、例えば、加熱して乾燥させてもよく、常温（例えば約２５℃）で自然乾燥させてもよい。加熱と自然乾燥の両方を組み合わせるのが好ましい。例えば、７０～９０℃、好ましくは８５℃～９５℃で、２０～４０分、好ましくは２５～３５分乾燥させた後、更に常温で４８時間以上、好ましくは６０～８０時間乾燥させることが好ましい。このような乾燥条件であれば、意図する性能を有する塗膜を形成させるのに十分である。 The drying means is not particularly limited, and for example, it may be dried by heating, or it may be naturally dried at room temperature (for example, about 25 ° C.). It is preferable to combine both heating and natural drying. For example, it is preferably dried at 70 to 90 ° C., preferably 85 ° C. to 95 ° C. for 20 to 40 minutes, preferably 25 to 35 minutes, and then further dried at room temperature for 48 hours or more, preferably 60 to 80 hours. .. Such drying conditions are sufficient to form a coating film having the intended performance.
　形成される塗膜は、例えば、１．４×１０-3～１．７×１０-3ｍｏｌ／ｍＬ、好ましくは１．５×１０-3～１．７×１０-3ｍｏｌ／ｍＬの架橋密度を有する。架橋密度が上記範囲内であれば、基材に対する付着性並びに耐乳酸性及び耐オレイン酸性に優れる。架橋密度は、ＲＳＡ－Ｇ２（ＴＡ ｉｎｓｔｒｕｍｅｎｔｓ社製）を用いて所定の条件下で測定される平坦領域貯蔵弾性率及びその絶対温度に基づき、以下の式に基づいて求めることができる。
　ｎ＝Ｅ’/３ＲＴ
　ｎ：架橋密度（ｍｏｌ／ｍＬ）（１／ｎ：架橋間分子量）
　Ｒ：気体定数（８．３１×１０６ Ｐａ・ｃｃ/ｍｏｌ・Ｋ）
　Ｔ：平坦領域貯蔵弾性率の絶対温度（Ｋ）
　Ｅ’：平坦領域貯蔵弾性率（Ｐａ） The coating film formed is, for example, a crosslink of 1.4 × 10 -3 to 1.7 × 10 -3 mol / mL, preferably 1.5 × 10 -3 to 1.7 × 10 -3 mol / mL. Has density. When the cross-linking density is within the above range, the adhesion to the substrate, the lactic acid resistance, and the olein acid resistance are excellent. The crosslink density can be determined based on the flat region storage elastic modulus measured under predetermined conditions using RSA-G2 (manufactured by TA instruments) and its absolute temperature, based on the following formula.
n = E'/ 3RT
n: Crosslink density (mol / mL) (1 / n: Molecular weight between crosslinks)
R: Gas constant (8.31 × 106 Pa · cc / mol · K)
T: Absolute temperature (K) of flat area storage elastic modulus
E': Flat area storage modulus (Pa)
　また、塗膜は、Ｏｗｅｎｓ－Ｗｅｎｄｔ式から算出される表面自由エネルギーが、５０ｍＮ／ｍ以上、例えば６０～８０ｍＮ／ｍであることが好ましい。Ｏｗｅｎｓ－Ｗｅｎｄｔ式とは、下記に示される表面自由エネルギーの理論式のひとつであり、固体の未知の表面自由エネルギー（γd S＋γp S）を、表面自由エネルギーが既知である２種の液体との接触角の測定値から算出することができる

　　　γL（１＋ｃｏｓθ）＝２（γd Sγd L）1/2＋２（γp Sγp L）1/2
　γL：液体表面自由エネルギー（既知）
　γd S：固体表面自由エネルギー　分散成分
　γd L：液体表面自由エネルギー　分散成分（既知）
　γp S：固体表面自由エネルギー　極性成分
　γp L：液体表面自由エネルギー　極性成分（既知）
　θ：接触角（測定値）

　本発明の場合、塗膜が、式中の表面自由エネルギーが未知である固体に該当し、接触角を測定する２種の液体が、式中の表面自由エネルギーが既知である液体に該当する。表面自由エネルギーが上記範囲内であれば、汗や皮脂が塗膜表面に対して濡れ広がりやすく、汗や皮脂による塗膜へのダメージを分散することができる。 Further, the coating film preferably has a surface free energy calculated from the Owns-Wendt equation of 50 mN / m or more, for example, 60 to 80 mN / m. The Owns-Wend formula is one of the theoretical formulas of the surface free energy shown below, and the unknown surface free energy (γ d S + γ p S ) of a solid is used as two kinds of liquids whose surface free energy is known. Can be calculated from the measured value of the contact angle with

γ L (1 + cos θ) = 2 (γ d S γ d L ) 1/2 + 2 (γ p S γ p L ) 1/2
γ L : Liquid surface free energy (known)
γ d S : Solid surface free energy dispersion component γ d L : Liquid surface free energy dispersion component (known)
γ p S : Solid surface free energy Polar component γ p L : Liquid surface free energy Polar component (known)
θ: Contact angle (measured value)

In the case of the present invention, the coating film corresponds to a solid in which the surface free energy in the formula is unknown, and the two liquids for measuring the contact angle correspond to liquids in which the surface free energy in the formula is known. When the surface free energy is within the above range, sweat and sebum easily wet and spread on the surface of the coating film, and damage to the coating film due to sweat and sebum can be dispersed.
　水性塗料組成物を塗布する基材は特に限定されず、基材の用途に応じて、様々な種類及び形状のものを選択することができる。基材としては、例えば、ＰＰＥ（ポリフェニレンエーテル）系樹脂、ポリスチレン系樹脂、ポリプロピレン、ポリエチレン等のオレフィン系重合体；ポリカーボネート樹脂；ポリメチルメタクリレート等のアクリル樹脂及びＡＢＳ樹脂等のプラスチック基材が挙げられる。 The base material to which the water-based coating composition is applied is not particularly limited, and various types and shapes can be selected depending on the use of the base material. Examples of the base material include olefin-based polymers such as PPE (polyphenylene ether) resin, polystyrene-based resin, polypropylene and polyethylene; polycarbonate resin; acrylic resin such as polymethylmethacrylate and plastic base material such as ABS resin. ..
　本発明はまた、基材と、基材の表面上の塗膜とを含む塗装物に関し、前記塗膜は、本発明の上記水性塗料組成物を塗装して形成されたものである。 The present invention also relates to a coating material containing a base material and a coating film on the surface of the base material, and the coating film is formed by coating the above-mentioned water-based coating composition of the present invention.
　本発明の塗料組成物は、各種の無機物、金属、木材、プラスチック等の様々な基材に適応できる。本発明の塗装物は、耐乳酸性及び耐オレイン酸性に優れるため、人の肌や手が長時間接触するようなプラスチック成形品、具体的には、自動車及び二輪車の内装部材及び外装部材、オーディオ、ビデオ、テレビ等の家電製品用部材、携帯電話、プリンター、パソコン等の事務機器用部材に特に有用である。 The coating composition of the present invention can be applied to various substrates such as various inorganic substances, metals, woods, and plastics. Since the coating material of the present invention is excellent in lactic acid resistance and olein acid resistance, it is a plastic molded product that comes into contact with human skin or hands for a long time, specifically, interior and exterior members of automobiles and motorcycles, audio equipment. It is particularly useful for parts for home appliances such as video and television, and parts for office equipment such as mobile phones, printers, and personal computers.
＜塗料調製＞
　表１に示される配合で主剤の原料を混合し、ディスパーで１０分間撹拌し、実施例１～３及び比較例１～５の主剤を調製した。実施例１～３のいずれの主剤においても、ポリカーボネート系ポリウレタンは３０ｎｍの平均粒子径を有する分散粒子として存在し、ポリエステル樹脂は水中に溶解していた。その後、調製した主剤に、表１に示される配合で各々の硬化剤を加え、ディスパーでさらに５分間撹拌し、実施例１～３及び比較例１～５の水性塗料組成物をそれぞれ調製した。 <Paint preparation>
The raw materials of the main agent were mixed according to the formulations shown in Table 1 and stirred with a disper for 10 minutes to prepare the main agents of Examples 1 to 3 and Comparative Examples 1 to 5. In any of the main agents of Examples 1 to 3, the polycarbonate-based polyurethane was present as dispersed particles having an average particle size of 30 nm, and the polyester resin was dissolved in water. Then, each curing agent was added to the prepared main agent according to the formulation shown in Table 1, and the mixture was further stirred with a disper for 5 minutes to prepare the aqueous coating compositions of Examples 1 to 3 and Comparative Examples 1 to 5, respectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
※１：ダイセル・オルネクス社製、ディスパージョン（平均粒子径３０ｎｍ）、固形分３７％ （含有水分５６％）、ワニスＯＨ価７０．３ｍｇＫＯＨ／ｇ（固形分換算１９０ｍｇＫＯＨ／ｇ）
※２：ダイセル・オルネクス社製、固形分６５％（含有水分０％）、ワニスＯＨ価１０６（固形分換算１６３ｍｇＫＯＨ／ｇ）
※３：住化コベストロウレタン社製：固形分４５％（含有水分４６％）、ワニスＯＨ価４９．５（固形分換算１１０ｍｇＫＯＨ／ｇ）
※４：トーヨーカラー社製カーボンブラック：顔料分20%（含有水分６０％）
※５：ジメチルエタノールアミン
※６：ビックケミージャパン社製
※７：ビックケミージャパン社製
※８：ジプロピレングリコールモノメチルエーテル
※９：住化コベストロウレタン社製、固形分１００％、イソシアネート基含有率２１．２％、酸価１０ｍｇＫＯＨ／ｇ
※１０：住化コベストロウレタン社製、固形分１００％ * 1: Made by Daicel Ornex, dispersion (average particle size 30 nm), solid content 37% (moisture content 56%), varnish OH value 70.3 mgKOH / g (solid content equivalent 190 mgKOH / g)
* 2: Made by Daicel Ornex, solid content 65% (moisture content 0%), varnish OH value 106 (solid content equivalent 163 mgKOH / g)
* 3: Made by Sumika Covestro Urethane: Solid content 45% (moisture content 46%), varnish OH value 49.5 (solid content conversion 110 mg KOH / g)
* 4: Carbon black manufactured by Toyo Color Co., Ltd .: Pigment content 20% (moisture content 60%)
* 5: Dimethylethanolamine * 6: Made by Big Chemy Japan * 7: Made by Big Chemy Japan * 8: Dipropylene glycol monomethyl ether * 9: Made by Sumika Cobestrolurethane, 100% solid content, isocyanate group content 21.2%, acid value 10 mgKOH / g
* 10: Made by Sumika Covestro Urethane, 100% solid content
＜試験片作成＞
　上記で調製した各水性塗料組成物を、スプレー塗装に適した粘度に脱イオン水で希釈後、ＡＢＳ－ＰＣ樹脂板にエアスプレー塗装で、乾燥塗膜の厚さが３０±５μｍになるよう塗装後、８０℃で３０分間乾燥し、さらに常温にて７２時間静置してそれぞれの試験片を得た。 <Preparation of test pieces>
Each water-based coating composition prepared above is diluted with deionized water to a viscosity suitable for spray coating, and then coated on an ABS-PC resin plate by air spray coating so that the thickness of the dry coating film is 30 ± 5 μm. Then, it was dried at 80 ° C. for 30 minutes, and further allowed to stand at room temperature for 72 hours to obtain each test piece.
　得られた各試験片について、以下の評価を行った。結果を表２に示す。 The following evaluations were performed on each of the obtained test pieces. The results are shown in Table 2.
＜外観評価＞
　ブツ、ワレ、シワ、ハジキ、ハガレ、フクレなどの塗膜異常の有無を目視で確認した。 <Appearance evaluation>
The presence or absence of coating film abnormalities such as bumps, cracks, wrinkles, repellents, peelings, and blisters was visually confirmed.
＜付着性評価＞
　ＪＩＳ　Ｋ　５６００－５－６（クロスカット法）に準じて、塗装後の塗膜に２ｍｍ角の碁盤目１０×１０マスの切り込みを入れ、碁盤目部分にセロハンテープを貼着し、急激に剥がした後に、塗面に残ったゴバン目塗膜の数を評価した。
　○：剥離塗膜なし
　△：切れ込みに沿って一部塗膜の欠落が見られる
　×：塗膜の剥離が見られる <Adhesiveness evaluation>
According to JIS K 5600-5-6 (cross-cut method), make a notch of 2 mm square grid 10 x 10 squares in the coating film after painting, attach cellophane tape to the grid, and peel it off rapidly. After that, the number of Goban-grained coating films remaining on the coated surface was evaluated.
◯: No peeling coating film △: Part of the coating film is missing along the notch ×: The coating film is peeled off
＜耐乳酸性評価＞
　試験片に１０％乳酸水溶液を０．２ｍｌ滴下し、８０±２℃で２４時間放置した後、ガーゼで拭き取り、セロハンテープを密着して剥離した。
　○：塗膜に変色、しみ、膨潤、軟化、剥がれなどの異常がない
　△：塗膜に若干の変色、膨潤、軟化などが見られる
　×：塗膜に著しい膨潤、軟化又は剥離が見られる <Lactate resistance evaluation>
0.2 ml of a 10% lactic acid aqueous solution was added dropwise to the test piece, and the mixture was left at 80 ± 2 ° C. for 24 hours, wiped off with gauze, and the cellophane tape was adhered and peeled off.
◯: No abnormality such as discoloration, stain, swelling, softening, or peeling of the coating film Δ: Slight discoloration, swelling, softening, etc. of the coating film ×: Significant swelling, softening, or peeling of the coating film
＜耐オレイン酸性評価＞
　試験片に１０％オレイン酸石油ベンジン溶液を０．２ｍｌ滴下し、８０±２℃で２４時間放置した後、ガーゼで拭き取り、セロハンテープを密着して剥離した。
　○：塗膜に変色、しみ、膨潤、軟化、剥がれなどの異常がない
　△：塗膜に若干の変色、膨潤、軟化などが見られる
　×：塗膜に著しい膨潤、軟化又は剥離が見られる <Olein acid resistance evaluation>
0.2 ml of a 10% oleic acid petroleum benzine solution was added dropwise to the test piece, left at 80 ± 2 ° C. for 24 hours, wiped off with gauze, and the cellophane tape was adhered and peeled off.
◯: No abnormality such as discoloration, stain, swelling, softening, peeling, etc. in the coating film Δ: Slight discoloration, swelling, softening, etc. are observed in the coating film ×: Significant swelling, softening or peeling is observed in the coating film
＜架橋密度＞
　ＲＳＡ－Ｇ２（ＴＡ　ｉｎｓｔｒｕｍｅｎｔｓ社製）を用いて下記の条件下で測定される平坦領域貯蔵弾性率及びその絶対温度に基づき、以下の式に基づいて求めた。
　～測定条件～
　周波数：１Ｈｚ
　歪み：０．０５％
　温度範囲：－５０～２００℃
　昇温速度：５℃／ｍｉｎ
　測定長さ：２４ｍｍ
　幅：８ｍｍ

　～算出式～
　ｎ＝Ｅ’/３ＲＴ
　ｎ：架橋密度（ｍｏｌ／ｍＬ）（１／ｎ：架橋間分子量）
　Ｒ：気体定数（８．３１×１０６ Ｐａ・ｃｃ/ｍｏｌ・Ｋ）
　Ｔ：平坦領域貯蔵弾性率の絶対温度（Ｋ）
　Ｅ’：平坦領域貯蔵弾性率（Ｐａ） <Crosslink density>
It was determined based on the following formula based on the flat region storage elastic modulus and its absolute temperature measured under the following conditions using RSA-G2 (manufactured by TA instruments).
~ Measurement conditions ~
Frequency: 1Hz
Distortion: 0.05%
Temperature range: -50 to 200 ° C
Heating rate: 5 ° C / min
Measurement length: 24 mm
Width: 8mm

~ Calculation formula ~
n = E'/ 3RT
n: Crosslink density (mol / mL) (1 / n: Molecular weight between crosslinks)
R: Gas constant (8.31 × 106 Pa · cc / mol · K)
T: Absolute temperature (K) of flat area storage elastic modulus
E': Flat area storage modulus (Pa)
＜塗膜の表面自由エネルギー＞
　塗装後の塗膜表面に、蒸留水を１滴滴下したときの接触角と、流動パラフィンを１滴滴下したときの接触角の値から、Ｏｗｅｎｓ－Ｗｅｎｄｔ式を用いて、塗膜の表面自由エネルギーを算出した。 <Free energy on the surface of the coating film>
From the value of the contact angle when one drop of distilled water is dropped and the value of the contact angle when one drop of liquid paraffin is dropped on the surface of the coating film after painting, the surface free energy of the coating film is used using the Owns-Wendt formula. Was calculated.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の塗料組成物は、自動車及び二輪車の内装部材及び外装部材、オーディオ、ビデオ、テレビ等の家電製品用部材、携帯電話、プリンター、パソコン等の事務機器用部材用の塗料として特に有用である。 The coating composition of the present invention is particularly useful as a coating material for interior and exterior members of automobiles and motorcycles, members for home appliances such as audio, video and television, and members for office equipment such as mobile phones, printers and personal computers. ..

Claims (14)

  1. 　主剤と硬化剤とを含む２液型塗料組成物であって、
    　前記主剤が、（Ａ）ポリカーボネート系ポリウレタン、（Ｂ）ポリエステル樹脂、及び水を含み、前記（Ａ）ポリカーボネート系ポリウレタンが、０．０１～０．１μｍの平均粒子径を有し、前記（Ｂ）ポリエステル樹脂が、０．０１μｍ以下の平均粒子径を有し、
    　前記硬化剤が、（Ｃ）親水性ポリイソシアネート化合物を含み、
    　前記（Ｃ）親水性ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と、前記（Ａ）ポリカーボネート系ポリウレタン及び前記（Ｂ）ポリエステル樹脂中の水酸基（ＯＨ）のモル比ＮＣＯ／ＯＨが、１．６～２．０である、
    ２液型塗料組成物。     A two-component paint composition containing a main agent and a curing agent.
    The main agent contains (A) polycarbonate-based polyurethane, (B) polyester resin, and water, and the (A) polycarbonate-based polyurethane has an average particle size of 0.01 to 0.1 μm, and the (B) The polyester resin has an average particle size of 0.01 μm or less and has an average particle size of 0.01 μm or less.
    The curing agent contains (C) a hydrophilic polyisocyanate compound.
    The molar ratio NCO / OH of the isocyanate group (NCO) in the (C) hydrophilic polyisocyanate compound and the hydroxyl group (OH) in the (A) polycarbonate-based polyurethane and the (B) polyester resin is 1.6 to. 2.0
    Two-component paint composition.
  2. 　前記（Ｂ）ポリエステル樹脂の水酸基価が、１００～２００ｍｇＫＯＨ／ｇである、請求項１に記載の２液型塗料組成物。 The two-component coating composition according to claim 1, wherein the polyester resin (B) has a hydroxyl value of 100 to 200 mgKOH / g.
  3. 　前記（Ｃ）親水性ポリイソシアネート化合物のイソシアネート基含有率が、１５～２５％である、請求項１又は２に記載の２液型塗料組成物。 The two-component coating composition according to claim 1 or 2, wherein the (C) hydrophilic polyisocyanate compound has an isocyanate group content of 15 to 25%.
  4. 　前記（Ａ）ポリカーボネート系ポリウレタンと前記（Ｂ）ポリエステル樹脂の固形分質量比が、８：２～６：４である、請求項１～３のいずれか１項に記載の２液型塗料組成物。 The two-component coating composition according to any one of claims 1 to 3, wherein the solid content mass ratio of the (A) polycarbonate-based polyurethane and the (B) polyester resin is 8: 2 to 6: 4. ..
  5. 　前記主剤が、カーボンブラック、金属顔料及び有機顔料からなる群から選択される着色剤を更に含む、請求項１～４のいずれか１項に記載の２液型塗料組成物。 The two-component coating composition according to any one of claims 1 to 4, wherein the main agent further contains a colorant selected from the group consisting of carbon black, metal pigments and organic pigments.
  6. 　請求項１～５のいずれか１項に記載の２液型塗料組成物の前記主剤と前記硬化剤とを配合してなる、水性塗料組成物。 A water-based paint composition obtained by blending the main agent and the curing agent of the two-component paint composition according to any one of claims 1 to 5.
  7. 　請求項６に記載の水性塗料組成物を塗装して形成された塗膜。 A coating film formed by coating the water-based coating composition according to claim 6.
  8. 　架橋密度が、１．４×１０-3～１．７×１０-3ｍｏｌ／ｍＬである、請求項７に記載の塗膜。 The coating film according to claim 7, wherein the crosslink density is 1.4 × 10 -3 to 1.7 × 10 -3 mol / mL.
  9. 　Ｏｗｅｎｓ－Ｗｅｎｄｔ式から算出される表面自由エネルギーが、５０ｍＮ／ｍ以上である、請求項７又は８に記載の塗膜。 The coating film according to claim 7 or 8, wherein the surface free energy calculated from the Owns-Wend formula is 50 mN / m or more.
  10. 　基材と、前記基材の表面上の請求項７～９のいずれか１項に記載の塗膜とを含む、塗装物。 A coated product containing the base material and the coating film according to any one of claims 7 to 9 on the surface of the base material.
  11. 　前記基材が、プラスチックである、請求項１０に記載の塗装物。 The coated material according to claim 10, wherein the base material is plastic.
  12. 　基材の塗装方法であって、以下の工程、
    　請求項１～５のいずれか１項に記載の２液型塗料組成物の前記主剤と前記硬化剤とを混合して、水性塗料組成物を得る工程、
    　前記水性塗料組成物を基材の表面に塗布する工程、
    　前記塗布した水性塗料組成物を乾燥させて塗膜を形成する工程、
    を含む、方法。     The method of painting the base material, which is the following process,
    A step of mixing the main agent and the curing agent of the two-component coating composition according to any one of claims 1 to 5 to obtain an aqueous coating composition.
    The step of applying the water-based coating composition to the surface of the base material,
    The step of drying the applied aqueous coating composition to form a coating film,
    Including methods.
  13. 　前記乾燥を、７０℃～９０℃で２０～４０分、続いて常温で４８時間以上行う、請求項１２に記載の方法。 The method according to claim 12, wherein the drying is carried out at 70 ° C. to 90 ° C. for 20 to 40 minutes, and then at room temperature for 48 hours or more.
  14. 　前記塗膜が、２５μｍ～４５μｍの厚さを有する、請求項１２又は１３に記載の塗装方法。 The coating method according to claim 12 or 13, wherein the coating film has a thickness of 25 μm to 45 μm.
PCT/JP2020/037276 2019-09-30 2020-09-30 Two-part coating material composition and coated article WO2021066055A1 (en)

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