WO2013047385A1 - Pâte de dispersion de pigment, composition de revêtement, procédé de formation d'un film de revêtement et article revêtu - Google Patents

Pâte de dispersion de pigment, composition de revêtement, procédé de formation d'un film de revêtement et article revêtu Download PDF

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WO2013047385A1
WO2013047385A1 PCT/JP2012/074277 JP2012074277W WO2013047385A1 WO 2013047385 A1 WO2013047385 A1 WO 2013047385A1 JP 2012074277 W JP2012074277 W JP 2012074277W WO 2013047385 A1 WO2013047385 A1 WO 2013047385A1
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resin
mass
coating film
parts
pigment dispersion
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PCT/JP2012/074277
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English (en)
Japanese (ja)
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敦史 塚本
耕 吉田
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関西ペイント株式会社
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Priority claimed from JP2011214800A external-priority patent/JP2014237731A/ja
Priority claimed from JP2011287406A external-priority patent/JP2014237067A/ja
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
Publication of WO2013047385A1 publication Critical patent/WO2013047385A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/644—Aluminium treated with organic compounds, e.g. 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/006—Metal
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)

Definitions

  • the present invention is a pigment dispersion paste containing a specific aluminum pigment and excellent in storage stability, and has good adhesion to the base material and good concealability capable of suppressing light transmission that induces deterioration of the base material.
  • the present invention relates to a coating composition containing a pigment dispersion paste capable of forming a coating film.
  • coating films for articles used in outdoor environments for a long time are required to be capable of suppressing light transmission that induces deterioration to the base material, such as aluminum.
  • the composition of pigment dispersion paste obtained by dispersing fine metal particles such as pigments, ultraviolet absorbers, light stabilizers, and other pigment components with a dispersant and the paint composition containing the pigment dispersion paste I have done it.
  • a metal reflective film-forming paint characterized by dispersing metal fine particles having an average primary particle diameter of 1 to 50 nm and a metal reflective film-forming paint are used. It is disclosed that a metal reflective film and a coated article provided with the metal reflective film can be obtained (Patent Document 1). Further, a multilayer coating film forming method is disclosed in which a dry coating film of 8 to 20 ⁇ m is formed using a composition containing a plate-like metal pigment having a thickness of 10 to 100 nm (Patent Document 2).
  • the problem to be solved by the present invention is to form a coating film that has excellent storage stability, good adhesion to the base material, and suppresses light transmission that induces deterioration to the base material and has excellent concealability. It is possible to provide a coating composition, a method for forming a coating film, a coated article, and a pigment dispersion paste used in the coating composition.
  • the present inventors have found that the problem can be achieved by a specific pigment dispersion paste and the specific coating composition containing the pigment dispersion paste, the hydroxyl group-containing resin (c1), and the crosslinking agent (d). I found it.
  • the pigment dispersion paste is 0.1% or less:
  • Monomer mixture of 0.1 to 10% by mass of the polymerizable unsaturated monomer (a1), 10 to 60% by mass of the hydroxyl group-containing polymerizable unsaturated monomer (a2), and 30 to 80% by mass of the other polymerizable unsaturated monomer (a3) A resin obtained by radical copolymerization.
  • Monomer mixture of 0.1 to 10% by mass of the polymerizable unsaturated monomer (a1), 10 to 60% by mass of the hydroxyl group-containing polymerizable unsaturated monomer (a2), and 30 to 80% by mass of the other polymerizable unsaturated monomer (a3) A resin obtained by radical copolymerization.
  • Item 3 The paint according to Item 2, which contains 0.1 to 30 parts by mass of barium sulfate (e) having an average particle diameter of 1 ⁇ m or less with respect to 100 parts by mass of the solid content of the hydroxyl group-containing resin (c1) and the crosslinking agent (d). Composition.
  • Item 4. The coating composition according to Item 2 or 3, comprising 1 to 100 parts by mass of ultrafine titanium dioxide (f) with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (c1) and the crosslinking agent (d).
  • Item 5 A method for forming a coating film by applying at least one top coating composition on a coating film obtained by applying the coating composition according to any one of Items 2 to 4.
  • Item 6. A coated article obtained by coating the coating composition according to any one of items 2 to 4.
  • Item 7 A method of forming a coating film (i) by coating a coating composition (I) having the following characteristics on an article to which a primer coating film may be applied, wherein the coating film (i) is dried
  • the coating film thickness is 1 to 15 ⁇ m
  • the content of the aluminum pigment (b) is 0.3 to 1.5 g / m 2
  • the light transmittance is 1% or less at any wavelength of 300 to 700 nm.
  • Coating film forming method Coating composition (I): pigment dispersion paste containing pigment dispersion resin (a) and aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less, base resin (c), A coating composition containing a crosslinking agent (d), wherein the amount of pigment dispersing resin (a) is 1 to 50 parts by mass relative to 100 parts by mass in total of the solid content of the base resin (c) and the crosslinking agent (d) A coating composition containing 2 to 40 parts by mass of the aluminum pigment (b).
  • Item 8 Polymerizability in which the pigment dispersion resin (a) contains at least one functional group selected from a phosphoric acid group, a quaternary ammonium base, a sulfonic acid group, and an amino group with respect to the total amount of all the constituent monomers.
  • Item 8 The method for forming a coating film according to Item 7, which is a resin obtained by radical copolymerization.
  • the coating composition (I) contains 0.1 to 30 parts by mass of barium sulfate (e) having an average particle diameter of 1 ⁇ m or less with respect to 100 parts by mass in total of the solid contents of the base resin (c) and the crosslinking agent (d).
  • Item 10 Any of Items 7 to 9, wherein the coating composition (I) contains 1 to 100 parts by mass of the fine particle titanium dioxide (f) with respect to 100 parts by mass in total of the solid contents of the base resin (c) and the crosslinking agent (d).
  • Item 11 The method for forming a coating film according to any one of Items 7 to 10, wherein the cured coating film by the coating composition (I) has an L value of 40 to 80 based on the CIE color matching function.
  • Item 12. A coated article formed by coating a coating film obtained by the coating film forming method according to any one of Items 7 to 11 with at least one overcoating paint.
  • the present invention is excellent in the storage stability of the pigment dispersion paste. Furthermore, the coating film obtained by applying the coating composition of the present invention has good adhesion to the base material and has a concealing property capable of suppressing light transmission that induces deterioration to the base material. For this reason, the multilayer coating film with favorable weather resistance can be obtained. Furthermore, the multilayer coating film obtained by recoating the top coating film on the lower coating film obtained by applying the coating composition of the present invention is obtained by the multilayer coating obtained by the design of the lower coating film through the top coating film. There is no adverse effect on the design of the film.
  • Pigment dispersion paste and coating composition In the first embodiment, the present invention provides a specific pigment dispersion paste and a coating composition containing the pigment dispersion paste. Details will be described below.
  • the pigment dispersion paste of the present invention is a pigment dispersion paste comprising a pigment dispersion resin (a), an aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less, and an organic solvent, A dry coating film having a thickness of 6 ⁇ m containing 5 to 100 parts by weight of the aluminum pigment (b) per 100 parts by weight of the solid content of the dispersing resin (a) and having a thickness of 300 to 700 nm obtained by applying the pigment dispersion paste.
  • the light transmittance is 0.1% or less. Regarding the light transmittance, it is as described later (Note 4).
  • the pigment dispersing resin (a) is at least one selected from an amino group, a quaternary ammonium base, a sulfonic acid group, and a phosphoric acid group with respect to the total amount of all the constituent monomers. Obtained by radical copolymerization of a monomer mixture containing a polymerizable unsaturated monomer (a1) containing a hydrophilic functional group, a hydroxyl group-containing polymerizable unsaturated monomer (a2), and another polymerizable unsaturated monomer (a3). It is done.
  • the pigment dispersing resin (a) may be neutralized.
  • Examples of the polymerizable unsaturated monomer (a1) containing a hydrophilic functional group include aminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate.
  • a sulfonic acid group-containing polymerizable monomer in which a resin for pigment dispersion copolymerized using a saturated monomer is excellent in storage stability can be obtained.
  • a coating composition using the pigment-dispersed paste is excellent in stability, and a coating film obtained by applying the coating composition is excellent in adhesion and weather resistance.
  • Hydroxyl group-containing polymerizable unsaturated monomer (a2) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol , Monoethers of polyether polyols such as polypropylene glycol and polybutylene glycol and hydroxyl group-containing polymerizable unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; ⁇ , ⁇ -unsaturated carboxylic acid and Cardura E10 (Japan Epoxy) Resin), adducts with monoepoxy compounds such as ⁇ -olefin epoxides; ⁇ -caprolactone-modified vinyl monomers obtained by ring-opening polymerization of ⁇ -caprolactone to 2-hydroxyethyl (meth) acrylate, such as “Plaxel FA-1,” “Plaxel FA-2
  • polymerizable unsaturated monomers (a3) are used as necessary.
  • Amino group-containing (meth) acrylamide compound 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 4- (meth) acryloyloxy-1,2,2,6,6-penta UV-absorbing functional group or UV-stable functional group-containing vinyl compound such as methylpiperidine; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, cyclohexanedimethanol mono Monoesterified products of polyhydric alcohols such as (meth) acrylate, N-hydroxyethyl (meth) acrylamide, polyethylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid, and reaction of these with ⁇ -caprolactone Hydroxyl group-containing vinyl compounds such as products; carboxyl group-containing vinyl compounds such as acrylic acid, methacryl
  • the blending amount of the polymerizable unsaturated monomer (a1) is 0.1 to 10% by mass, preferably 1 to 8% by mass, based on the total amount of all monomer components constituting the pigment dispersing resin (a).
  • the storage stability of the pigment dispersion paste containing the aluminum pigment (b) and the adhesion to the base material in the coating film obtained by coating the coating composition containing the pigment dispersion paste Improvement It is preferable from the viewpoint of obtaining a coating film excellent in concealing properties that can suppress the light transmittance of inducing degradation of the fine ground material.
  • a pigment dispersion resin (a) is obtained by radical copolymerization of a monomer mixture comprising the polymerizable unsaturated monomer (a1), the hydroxyl group-containing polymerizable unsaturated monomer (a2) and the other polymerizable unsaturated monomer (a3).
  • the method include a bulk polymerization method, a solution polymerization method, a bulk-suspension two-stage polymerization method in which suspension polymerization is performed after bulk polymerization, which are known polymerization methods.
  • the polymerization initiator a polymerization initiator generally used in a production method of an acrylic polymer or the like is used, and the amount thereof is usually polymerizable. It is in the range of 0.1 to 10% by mass with respect to the total amount of the unsaturated monomer (a1), the hydroxyl group-containing polymerizable unsaturated monomer (a2), and the other polymerizable unsaturated monomer (a3).
  • polymerization initiator examples include azo polymerization initiators such as 2,2′-azobisisobutylnitrile, azobis-2-methylbutyronitrile, azobisdivaleronitrile; t-butylperoxyisobutyrate, t -Butylperoxy-2-ethylhexanoate, t-amylperoxy 3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,2-bis (4,4-di-t-butyl Organic peroxide polymerization initiators such as peroxycyclohexyl) propane.
  • azo polymerization initiators such as 2,2′-azobisisobutylnitrile, azobis-2-methylbutyronitrile, azobisdivaleronitrile
  • t-butylperoxyisobutyrate t -Butylperoxy-2-ethylhexanoate
  • the solution polymerization method is particularly preferable.
  • the method by the solution polymerization method include a method in which the monomer mixture is dissolved or decomposed in an organic solvent and heated with stirring at a temperature of usually about 80 ° C. to 200 ° C. in the presence of a radical polymerization initiator. it can.
  • the reaction time is usually 1 to 10 hours.
  • organic solvent examples include hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral spirit; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether acetate; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol; n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene Ether solvents such as glycol monoethyl ether; SWAZOL 310, SWAZOL 1000, SWAZOL 15 manufactured by Cosmo Oil Co., Ltd. Aromatic
  • organic solvents can be used alone or in combination of two or more.
  • the organic solvent is usually 400 with respect to the total amount of the polymerizable unsaturated monomer (a1), the hydroxyl group-containing polymerizable unsaturated monomer (a2) and the other polymerizable unsaturated monomer (a3). It is used in the range of less than mass%.
  • the method of adding the monomer component and the polymerization initiator is not particularly limited, but the polymerization initiator is from the initial stage of polymerization to the late stage of polymerization rather than being charged all at the initial stage of polymerization. It is preferable from the point of suppression of formation of a defective cross-linked product.
  • the pigment dispersing resin (a) obtainable by the copolymerization reaction has a weight average molecular weight of 10,000 to 100,000, preferably 15,000 to 50,000. From the viewpoints of various performances of the coating film (for example, adhesion to the base material and weather resistance, surface that can fully exhibit the design of the top coating film, etc.), ease of handling of the resin (resin viscosity not significantly high), etc. Is appropriate.
  • the “weight average molecular weight” in the specification is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatograph according to the method described in JIS K 0124-83.
  • the gel permeation chromatograph “HLC8120GPC” (manufactured by Tosoh Corporation) was used.
  • the columns four columns of “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, “TSKgel G-2000HXL” (both manufactured by Tosoh Corporation) are used.
  • Mobile phase Tetrahydrofuran
  • measurement temperature 40 ° C.
  • flow rate 1 ml / min
  • detector under the conditions of RI.
  • the pigment dispersion paste of the present invention contains an aluminum pigment (b) having an average particle size of 20 to 150 nm and an aspect ratio of 7 or less (hereinafter sometimes abbreviated as “aluminum pigment (b)”).
  • aluminum pigment (b) having an average particle size of 20 to 150 nm and an aspect ratio of 7 or less
  • the aluminum metal is treated with a grinding aid and / or a passivating agent (passivator) as necessary, and the pigment dispersing resin (a) It can be obtained by pulverization and grinding using a specific dispersing means in the presence of a pulverizing medium liquid.
  • the presence of the pigment dispersing resin (a) and the grinding medium liquid is obtained without subjecting the aluminum metal to treatment with a grinding aid and / or a passivating agent (passivator). Then, it is obtained by grinding and grinding using a specific dispersing means, or the aluminum metal is treated with a grinding aid and / or a passivating agent (passivator), and the pigment dispersing resin ( a) It can be obtained by pulverization and grinding using a specific dispersing means in the presence of a pulverizing medium liquid.
  • the aluminum pigment (b) in order to obtain the aluminum pigment (b), in particular, it is difficult to form by a ball mill usually used for pigment dispersion, and if necessary, a grinding aid and / or Aluminum metal treated with a passivating agent (passivator), pigment dispersion resin (a), and a pulverizing medium liquid are mixed, and the above-mentioned is used using an ultra-fine pulverizer such as a planetary ball mill, a homogenizer, and a bead mill.
  • the average particle size within the range (Note 1) that is, the average particle size within the range of 20 to 150 nm, preferably 80 to 130 nm, more preferably 90 to 120 nm, and the average aspect ratio (Note 2) of 7 or less, It is preferably 5 or less, more preferably 2 or less, and it is dispersed in a more spherical aluminum pigment (b). Having an average particle diameter and an average aspect ratio in the above ranges is necessary to obtain a coating film excellent in concealability capable of suppressing adhesion of light to the base material to improve adhesion and deterioration of the base material.
  • a pigment dispersion paste can be obtained by dispersing aluminum metal for 0.5 to 96 hours, preferably 1 to 48 hours, more preferably 5 to 24 hours.
  • aliphatic amines, aliphatic amides and aliphatic alcohols are used in addition to higher fatty acids such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid.
  • the grinding medium liquid can be used without particular limitation as long as it can dissolve the pigment dispersing resin (a) and does not adversely affect the dispersion of the aluminum metal.
  • Ether solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, sec-butanol and isobutanol, n-butyl Ether, dioxane, ethylene glycol monomethyl ether, ethers such as ethylene glycol monoethyl ether, Cosmo Oil Co.
  • Swasol 310 can include Swasol 1000, aromatic petroleum solvent system such as Swasol 1500 and the like. These organic solvents can be used alone or in combination.
  • the content of the aluminum pigment (b) is 5 to 100 parts by weight, preferably 10 to 60 parts by weight, more preferably 100 parts by weight of the solid content of the pigment dispersion resin (a).
  • a range of 20 to 55 parts by mass is desirable for the stability of the pigment dispersion paste.
  • the blending amount of the aluminum pigment (b) is less than 5 parts by mass, the concealability of the base material by the obtained coating film is lowered, so that the surface of the base material is deteriorated by transmitting ultraviolet rays through the coating film. Adhesion with the material may be reduced. Moreover, when the compounding quantity of aluminum pigment (b) exceeds 100 mass parts, the stability of the pigment dispersion paste and the coating composition using this pigment dispersion paste may fall.
  • the coating composition will be described.
  • the coating composition of this invention contains the said pigment dispersion paste, hydroxyl-containing resin (c1), and a crosslinking agent (d).
  • the amount of pigment dispersing resin (a) is preferably 1 with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (c1) and the crosslinking agent (d).
  • the amount of the aluminum pigment (b) is 5 to 35 parts by mass, preferably 8 to 20 parts by mass, and optionally contains a solvent. Therefore, the coating composition of the present invention may contain a solvent.
  • the method for producing a coating composition comprises preparing a pigment dispersion paste in advance, mixing the pigment dispersion paste, the hydroxyl group-containing resin (c1) and the crosslinking agent (d), and a solvent as required, This is also preferable in order to obtain a coating film with good concealability and good concealability capable of suppressing light transmission that induces deterioration of the base material.
  • hydroxyl group-containing resin (c1) for example, a resin such as an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin, or a polyurethane resin having a functional group capable of crosslinking reaction can be suitably used.
  • the functional group capable of crosslinking reaction include a hydroxyl group, a carboxyl group, an epoxy group, and a carbonyl group.
  • acrylic resin, polyester resin, and the like are preferable from the viewpoint of weather resistance.
  • the acrylic resin usually has a hydroxyl value in the range of 50 to 600 mgKOH / g, an acid value in the range of 10 to 100 mgKOH / g, and a weight average molecular weight in the range of 1,000 to 100,000. It is preferable that The polyester resin usually preferably has a hydroxyl value in the range of 20 to 800 mgKOH / g, an acid value in the range of 4 to 200 mgKOH / g, and a weight average molecular weight in the range of 500 to 500,000.
  • the crosslinking agent (d) can be used without particular limitation as long as it can be cured by reacting with a hydroxyl group-containing resin by heating, and can be used without any limitation, such as a melamine resin, a benzoguanamine resin, Urea resins and blocked polyisocyanates can be used.
  • the melamine resin examples include a monohydric alcohol having 1 to 8 carbon atoms, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, in which a part or all of the methylol group of methylolated melamine is used. And partially etherified or fully etherified melamine resins etherified with i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
  • Examples of commercially available melamine resins include Cymel 202, Cymel 232, Cymel 235, Cymel 238, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, and Cymel 350. , Cymel 370, Cymel 701, Cymel 703, Cymel 1141 (manufactured by Nippon Cytec Industries, Inc.), Uban 20SE60 (manufactured by Mitsui Cytec Co., Ltd.), and the like.
  • the mixing ratio of the hydroxyl group-containing resin (c1) and the crosslinking agent (d) is based on 100 parts by mass of the solid content of both, and the hydroxyl group-containing resin (c1) 65 to 95 mass in terms of solid content. From the viewpoints of adhesion to the base material and curability, it is preferable that the amount is from 70 to 90 parts by weight, and preferably from 5 to 35 parts by weight, and preferably from 10 to 30 parts by weight of the crosslinking agent (d).
  • the coating composition of the present invention includes, as necessary, extender pigments such as clay, talc, barita, and calcium carbonate; aluminum tripolyphosphate, zinc molybdate, vanadium pentoxide, and the like.
  • extender pigments such as clay, talc, barita, and calcium carbonate; aluminum tripolyphosphate, zinc molybdate, vanadium pentoxide, and the like.
  • Anti-corrosive pigments white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indanthrene blue; green pigments such as cyanine green and patina; organic red pigments such as azo and quinacridone, bengara and bengara Red pigments such as benzimidazolone, isoindolinone, isoindoline and quinophthalone, yellow pigments such as titanium yellow, yellow lead and yellow iron oxide; carbon black, graphite, pine smoke, etc.
  • a coloring pigment such as a black pigment can be contained.
  • the coating composition may contain a curing catalyst.
  • the curing catalyst is blended as necessary to promote the reaction between the hydroxyl group-containing resin (c1) and the crosslinking agent (d).
  • the crosslinking agent (d) is an amino resin
  • a sulfonic acid is used.
  • a compound or a neutralized amine of a sulfonic acid compound is preferably used.
  • the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like.
  • the amine in the amine neutralized product of the sulfonic acid compound may be any of primary amine, secondary amine, and tertiary amine. Of these, an amine neutralized product of p-toluenesulfonic acid and / or an amine neutralized product of dodecylbenzenesulfonic acid is preferred from the viewpoints of coating stability, reaction promoting effect, and obtained coating film properties.
  • the curing catalyst includes tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanote), dioctyl Mention may be made of organometallic compounds such as tin diacetate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin trioctate, lead 2-ethylhexanoate and zinc octylate.
  • the curing catalyst is 0.1 to 5.0 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the total solid content of the hydroxyl group-containing resin (c1) and the crosslinking agent (d). Is suitable.
  • the coating composition of the present invention contains barium sulfate having an average particle diameter of 1 ⁇ m or less with respect to a total solid content of 100 parts by mass of the hydroxyl group-containing resin (c1) and the crosslinking agent (d).
  • e barium sulfate having an average particle diameter of 1 ⁇ m or less with respect to a total solid content of 100 parts by mass of the hydroxyl group-containing resin (c1) and the crosslinking agent (d).
  • e) in an amount of 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 8 parts by weight, a coating film having excellent adhesion to the base material can be obtained.
  • Examples of commercially available products include Varifine BF-10 and Varifine BF-20 (trade name, manufactured by Sakai Chemical Industry Co., Ltd.).
  • the ultrafine titanium dioxide (f) is 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 100 parts by weight of the total solid content of the hydroxyl group-containing resin (c1) and the crosslinking agent (d). By containing 8 to 60 parts by mass, a coating film excellent in design and finish can be obtained.
  • organic solvents such as hydrocarbon solvents, ester solvents, ether solvents, alcohol solvents, ketone solvents, and water can be used as dilution solvents.
  • the coating composition is Ford Cup No.
  • the coating is preferably carried out by adjusting the solid content concentration within the range of 20 to 60% by mass so that a viscosity in the range of 10 to 40 seconds can be obtained at 4 (20 ° C.).
  • the object to be coated is not particularly limited.
  • metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel; polyethylene resin, polypropylene resin, acrylonitrile -Butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and other plastic materials such as various FRPs; glass, cement, concrete and other inorganic materials; wood A fiber material (paper, cloth, etc.) and the like, among which a metal material and a plastic material are suitable.
  • the object to be coated is a material obtained by performing surface treatment such as phosphate treatment, chromate treatment, zirconium treatment, complex oxide treatment on the metal material or a metal surface such as a car body formed therefrom. May be. Furthermore, the electrodeposition coating and / or the powder coating may be made.
  • the use of the object to be coated is not particularly limited, and for example, an outer plate part of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part; an outer plate part of a home electric product such as a mobile phone or an audio device Among them, the outer plate part of an automobile body and automobile parts are preferable.
  • the coating composition of the present invention is applied by air spray, airless spray, rotary atomizing coater, dip coating, brush, curtain coating, roll coating, etc., with a cured film thickness of 1 to 30 ⁇ m, preferably 2 to 25 ⁇ m. More preferably, the coating is applied to a thickness of 4 to 15 ⁇ m and cured by baking and drying at 100 to 230 ° C. for 5 to 90 minutes, particularly at 120 to 160 ° C. for 10 to 40 minutes. Form a coating film.
  • a multilayer coating film can be formed by a coating film forming method such as the following method (I) to method (III).
  • a top coating (solid color) is applied by a method such as airless spraying, air spraying, rotary atomizing coating, etc.
  • 2-coat 2-bake method (2C2B) obtained by coating to 50 ⁇ m and heating at a baking temperature of about 100 to 180 ° C. for about 10 to 90 minutes; on the wet coating film of the coating composition of the present invention
  • 2-coat 1-bake method (2C1B) in which a top coat (solid color) is applied repeatedly by wet.
  • a dry film thickness is about 5 to 50 ⁇ m by a method such as airless spraying, air spraying, rotary atomizing coating, etc. on the cured coating film of the coating composition of the present invention. Painted so that it is wet-on-wet or cured, and a clear paint is applied so that the film thickness is about 5 to 70 ⁇ m, and the baking temperature is about 10 to 90 at about 60 to 160 ° C. 3 coat 2 bake method (3C2B), 3 coat 3 bake method (3C3B) formed by heating for a minute.
  • a dry film thickness of about 5 to 5 is applied on the wet coating film of the coating composition of the present invention by a method such as airless spraying, air spraying, rotary atomizing coating, and the like.
  • Apply to 50 ⁇ m, wet-on-wet or cure, apply clear paint to a cured film thickness of about 5-70 ⁇ m, and bake at about 60-160 °C Examples include, but are not limited to, a three-coat one-bake method (3C1B) and a three-coat two-bake method (3C2B) that are heated for 10 to 90 minutes.
  • the coating film obtained by applying the coating composition of the present invention preferably has an L value (Note 3) based on the CIE color matching function of 40 to 80, more preferably an L value of 45 to 65,
  • L value (Note 3)
  • the coating film by the coating composition of the present invention does not adversely affect the design properties of the top coating film. It is possible to provide a coated article having excellent finish of the coating film.
  • the coating film obtained by applying the coating composition of the present invention has a light transmittance (Note 4) of 1% or less for any 6 ⁇ m dry coating film having a wavelength of 300 to 700 nm, and a base material (for example, , An electrodeposition coating film, a powder coating film) and a multi-layer coating film excellent in concealability capable of suppressing light transmission that induces deterioration of the base material.
  • a light transmittance (Note 4) of 1% or less for any 6 ⁇ m dry coating film having a wavelength of 300 to 700 nm, and a base material (for example, , An electrodeposition coating film, a powder coating film) and a multi-layer coating film excellent in concealability capable of suppressing light transmission that induces deterioration of the base material.
  • L value Based on L * a * b * color system defined in JIS Z 8729 using MA68II (trade name, multi-angle spectrophotometer, manufactured by X-rite) as the test plate. This is a
  • the reason why the light transmittance can be set as described above is that the aluminum pigment (b) is dispersed throughout the cross section of the coating, as is apparent from the cross-sectional photograph of the obtained coating (FIG. 1). Since light transmission that induces deterioration more efficiently can be suppressed, it is possible to obtain a coating film having good adhesion to the base material and good concealment of the base material.
  • an aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less is contained in the coating film obtained by applying the coating composition of the present invention.
  • the 6 ⁇ m dry coating film obtained by applying the coating composition can have a light transmittance of 1% or less at any wavelength of 300 to 700 nm.
  • the present invention applies a coating composition (I) having the following characteristics on a coating to which a primer coating film may be applied.
  • the coating film forming method is characterized in that the light transmittance is 1% or less at any wavelength of 300 to 700 nm. Details will be described below.
  • Light transmittance A spectrophotometer UV is applied to a coating film obtained by coating each coating composition on a glass plate with the dry film thickness described in the table and drying at 140 ° C. for 20 minutes. The light transmittance at a wavelength of 300 to 700 nm was measured using -3100 (manufactured by Shimadzu Corporation), and the maximum value of the transmittance was defined as the light transmittance (%).
  • the coating composition (I) comprises a pigment dispersion resin (a), a pigment dispersion paste containing an aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less, a substrate A coating composition containing a resin (c) and a crosslinking agent (d), wherein the amount of pigment dispersion resin (a) is 100 parts by mass in total of the solid content of the base resin (c) and the crosslinking agent (d).
  • the method for producing the coating composition (I) comprises producing a pigment dispersion paste in advance, the pigment dispersion paste, the base resin (c), the crosslinking agent (d), and, if necessary, a solvent. It is also preferable to obtain a coating film having good concealability that can suppress light transmission that induces deterioration of the base material and has good adhesion to the base material.
  • a resin such as an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin, or a polyurethane resin having a specific functional group is used as the pigment dispersion resin (a) used in the pigment dispersion paste. it can.
  • the phosphate group and the quaternary ammonium are particularly suitable for the coating film forming method of the present invention with respect to the total amount of all the constituent monomers.
  • the pigment dispersion resin (a) obtained by radical copolymerization of the monomer mixture containing) is preferred from the viewpoint of the stability of the pigment dispersion paste and the coating film performance. Further, the obtained pigment dispersing resin (a) may be neutralized.
  • Examples of the polymerizable unsaturated monomer (a1) containing the specific functional group include those exemplified in the above [I]. These compounds (a1) can be used alone or in combination of two or more.
  • a pigment dispersion paste that is copolymerized using an acrylate monomer and a sulfonic acid group-containing polymerizable unsaturated monomer can provide a pigment dispersion paste having excellent storage stability.
  • a coating composition using the pigment-dispersed paste is excellent in stability, and a coating film obtained by applying the coating composition is excellent in adhesion and weather resistance.
  • Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a2) include those exemplified in the above [I]. These can be used alone or in combination of two or more.
  • polymerizable unsaturated monomers (a3) are used as necessary. Examples thereof include those exemplified in the above [I]. These can be used alone or in combination of two or more.
  • the pigment dispersion by radical copolymerization of a monomer mixture comprising the polymerizable unsaturated monomer (a1), the hydroxyl group-containing polymerizable unsaturated monomer (a2) and the other polymerizable unsaturated monomer (a3).
  • the blending amount and method exemplified in the above [I] can be appropriately employed.
  • pigment dispersion resin (a) by radical copolymerization examples include the conditions exemplified in the above [I].
  • the pigment dispersion paste used in the coating film forming method of the present invention is an aluminum pigment (b) (hereinafter referred to as “aluminum pigment (b)” having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less. May be abbreviated as “)”.
  • aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less. May be abbreviated as “)”.
  • aluminum pigment (b) having an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less. May be abbreviated as “)”.
  • a grinding aid and / or a passivating agent is used. Average particle size within the above range using a superfine pulverizer such as a planetary ball mill, a homogenizer, a bead mill, etc.
  • Diameter (Note 1) that is, an average particle diameter in the range of 20 to 150 nm, preferably 60 to 130 nm, more preferably 70 to 120 nm, and an average aspect ratio (Note 2) of 7 or less, more preferably 5 or less, Preferably, it is dispersed in a more spherical aluminum pigment (b) within the range of 2 or less.
  • a pigment dispersion paste can be obtained by dispersing aluminum metal in the presence for 0.5 to 96 hours, preferably 1 to 48 hours, more preferably 5 to 24 hours.
  • the preferable content of the aluminum pigment (b) in the grinding aid, the grinding medium liquid, and the pigment dispersion paste can also be exemplified in the above-mentioned [I]. .
  • the base resin (c) used in the second embodiment for example, an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin, a polyurethane resin, or the like having a functional group capable of crosslinking reaction is preferably used. It can.
  • the functional group include a hydroxyl group, a carboxyl group, an epoxy group, and a carbonyl group.
  • acrylic resin, polyester resin, and the like are preferable from the viewpoint of weather resistance.
  • the acrylic resin usually has a hydroxyl value in the range of 50 to 200 mgKOH / g, an acid value in the range of 10 to 100 mgKOH / g, and a weight average molecular weight in the range of 1,000 to 100,000. It is preferable that The polyester resin usually preferably has a hydroxyl value in the range of 20 to 300 mgKOH / g, an acid value in the range of 4 to 200 mgKOH / g, and a weight average molecular weight in the range of 500 to 500,000.
  • the crosslinking agent (d) can be used without particular limitation as long as it can be cured by reacting with the functional group of the base resin (c) by heating.
  • Resins, benzoguanamine resins, urea resins, blocked polyisocyanates, and the like can be used.
  • the melamine resin examples include those exemplified in the above [I].
  • the mixing ratio of the base resin (c) and the crosslinking agent (d) is 65 to 95 parts by weight of the base resin (c) based on a total solid content of 100 parts by weight. 70 to 90 parts by mass, and 5 to 35 parts by mass, preferably 10 to 30 parts by mass of the crosslinking agent (d) are preferable from the viewpoint of adhesion to the base material and curability of the coating film.
  • the content of the aluminum pigment (b) is 2 to 40 parts by mass, preferably 5 with respect to 100 parts by mass of the solid content of the base resin (c) and the crosslinking agent (d).
  • a range of ⁇ 25 parts by mass is desirable for coating stability and finish.
  • the blending amount of the aluminum pigment (b) is less than 2 parts by mass, the concealability of the base material by the obtained coating film is lowered, so that the surface of the base material is deteriorated by transmitting ultraviolet rays through the coating film. Adhesion with the material may be reduced. Moreover, when the compounding quantity of aluminum pigment (b) exceeds 40 mass parts, stability of a coating composition may fall.
  • the coating composition (I) may contain extender pigments; rust preventive pigments; colored pigments and the like listed in [I] as necessary. it can. Further, bright materials such as aluminum flakes and interference pearl pigments can also be contained.
  • the coating composition (I) used in the coating film forming method of the present invention may contain a curing catalyst.
  • the curing catalyst is blended as necessary to promote the reaction between the base resin (c) and the crosslinking agent (d).
  • the crosslinking agent (d) is an amino resin
  • a sulfonic acid compound is used.
  • an amine neutralized product of a sulfonic acid compound is preferably used.
  • Typical examples of the sulfonic acid compound include those exemplified in the above-mentioned [I].
  • the curing catalyst include the organometallic compounds exemplified in the above [I].
  • the curing catalyst is suitably 0.1 to 5.0 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the total solid content of the base resin (c) and the crosslinking agent (d). ing.
  • the coating composition (I) used in the coating film forming method of the present invention has a solid content of 100 mass in total of the base resin (c) and the crosslinking agent (d) as necessary. 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, and more preferably 2 to 8 parts by weight of barium sulfate (e) having an average particle diameter of 1 ⁇ m or less with respect to parts by weight. A coating film having excellent adhesion can be obtained.
  • Examples of commercially available barium sulfate (e) having an average particle diameter of 1 ⁇ m or less include Varifine BF-10 and Varifine BF-20 (above, trade name, manufactured by Sakai Chemical Industry Co., Ltd.).
  • the fine particle titanium dioxide may be added to the total solid content of 100 parts by mass of the base resin (c) and the crosslinking agent (d) as necessary. 1 to 100 parts by mass, preferably 5 to 80 parts by mass, and more preferably 8 to 60 parts by mass of (f) can be contained.
  • the fine particle titanium dioxide (f) has an average particle size of 10 to 80 nm, preferably 15 to 60 nm, and therefore has high transparency, and a coating film excellent in design can be obtained by the effect of scattering light.
  • Examples of commercially available products include MT-100SA (trade name, fine particle titanium dioxide, average particle diameter of 15 nm, manufactured by Teica Co., Ltd., trade name, fine particle titanium dioxide, average particle diameter of 50 nm, manufactured by MT-700HD Teica). .
  • the coating composition (I) those exemplified in the above [I] can be used as a diluent solvent. Next, a preferred embodiment of the coating using the coating composition (I) in the second embodiment will be described.
  • the object to be coated is not particularly limited, and examples thereof include those exemplified in the above [I].
  • the coating composition (I) is then applied by air spray, airless spray, rotary atomizer, dip coating, brush, curtain coating, roll coating, etc., and the cured film thickness is 1 to 15 ⁇ m, preferably 2 to 7 ⁇ m.
  • a cured coating film is formed by baking and drying at 100 to 230 ° C. for 5 to 90 minutes, particularly at 120 to 160 ° C. for 10 to 40 minutes. Further, if the cured film thickness exceeds 15 ⁇ m, sagging may occur in the vertical portion, which is not desirable.
  • a multilayer coating film can be formed by the methods (I) to (III) exemplified in the above [I]. .
  • the coating film obtained by coating the coating composition (I) preferably has an L value (Note 3) based on the CIE color matching function of 40 to 80, more preferably In the case where the L value is 45 to 65 and the top coat film is repeatedly applied to the top coat film, for example, even if the concealing power of the top coat film is inferior, the coat film by the coating composition (I) It is possible to provide a coated article that does not adversely affect the design properties and is excellent in the finish of the multilayer coating film.
  • the coating film (i) obtained by applying the coating composition (I) of the present invention has a dry coating film thickness of 1 to 15 ⁇ m and an aluminum pigment (b) content of 0.3 to 1. 5 g / m 2 , preferably 0.6 to 1.0 g / m 2 , and the coating film (i) has a light transmittance (see Note 26) of 1% or less at any wavelength of 300 to 700 nm, Preferably, it is 0.5% or less, and is a multi-layer coating film excellent in concealability capable of suppressing light transmission that induces adhesion to a base material (eg, electrodeposition coating film, powder coating film) and deterioration of the base material. Can be obtained.
  • the reason why the light transmittance can be set as described above is as described in [I] above.
  • the multi-layer coating film obtained by repeatedly applying the top coating film on the lower coating film obtained by coating the coating composition (I) has a design property of the lower coating film. There is no adverse effect on the design as a multilayer coating film through the coating film.
  • the coating film (i) obtained by coating the coating composition (I) has an average particle diameter of 20 to 150 nm and an average aspect ratio of 7 or less.
  • the aluminum pigment (b) is dispersed throughout the coating film, and the light transmittance can be 1% or less at any wavelength of 300 to 700 nm.
  • Production Example A1 Acrylic resin no. Production of A1 solution To a 4 liter flask equipped with a thermometer, reflux condenser, and stirrer was added 28 parts of Swazol 1000 (Cosmo Oil Co., Ltd., aromatic hydrocarbon organic solvent) and 85 parts of toluene.
  • Swazol 1000 Cosmo Oil Co., Ltd., aromatic hydrocarbon organic solvent
  • Acrylic resin No. 1 was prepared in the same manner as in Production Example A1 except that a monomer mixture having the composition shown in Table 1 was used. A2-No. An A10 solution was obtained. In addition, in Table 1, acrylic resin no. A2-No. The resin characteristic number of the resin solid content of A10 is shown.
  • JAMP-514M Mixture based on mono (2-hydroxyethyl methacrylate) phosphate, trade name, Johoku Chemical
  • Acryester DMC78 Mitsubishi Rayon Co., Ltd., trade name, methacryloyloxyethyltrimethylammonium chloride, quaternary ammonium base-containing unsaturated monomer
  • Plaxel FM-3 Daicel Chemical Industries, Ltd., trade name , 2-Hydroxyethyl methacrylate ⁇ -caprolactone modified vinyl monomer
  • Example A2 to A11 Except for the contents shown in Table 2, the same procedure as in Example A1 was carried out, and pigment dispersion paste No. A2-No. A11 was obtained. Furthermore, the storage stability of the obtained pigment dispersion paste was checked according to the following conditions.
  • Cymel 303 Nihon Cytec Industries, Ltd., trade name, methyl etherified melamine resin
  • Necure 5225 King Industries, Inc. (USA), trade name, neutralized amine solution of dodecylbenzenesulfonic acid
  • Examples A13 to A24 Coating composition No. A2-No. Production Example of A13 A coating composition No. A13 was prepared in the same manner as in Example A12 except that the blending contents shown in Table 4 were used. A2-No. A13 was obtained.
  • Comparative Examples A20, A21 Coating composition No. A24-No. Production Example of A25 A coating composition No. A25 was prepared in the same manner as in Comparative Example A19 except that the blending contents shown in Table 5 were used. A24, paint composition No. A25 was obtained.
  • Alpaste 7620NS manufactured by Toyo Aluminum Co., Ltd., trade name, aluminum flake pigment, average particle diameter 18 ⁇ m, aspect ratio 54.5
  • Alpaste 1950M manufactured by Toyo Aluminum Co., Ltd., trade name, aluminum flake pigment, average particle size 54 ⁇ m, aspect ratio 80.6
  • Alpaste MG600 manufactured by Toyo Aluminum Co., Ltd., trade name, aluminum flake pigment, average particle size 25 ⁇ m, aspect ratio 62.5
  • Test plate “Electron GT-10HT” trade name, amine-added epoxy resin / block polyisocyanate curing cationic electrodeposition coating
  • each coating composition No. obtained in Examples and Comparative Examples was used.
  • A1-No. A25 was applied to a dry film thickness of 6 ⁇ m and heated at 140 ° C. for 20 minutes for crosslinking and curing.
  • water-based metallic base coat WBC713T (manufactured by Kansai Paint Co., Ltd., trade name, acrylic / melamine resin-based paint) is applied to a dry film thickness of 8 ⁇ m (film thickness through which the base material is transparent), and the booth atmosphere (23 ° C., relative humidity 67%) For 1 minute and 30 seconds, followed by preliminary drying at 80 ° C. for 3 minutes.
  • Test results Tables 6 and 7 show the results of the test using each test plate according to the following test conditions.
  • Adhesion According to JIS K 5600-5-6 (1999) grid pattern-tape method, a knife is used to reach the substrate on the coating film surface of the test plate vertically at intervals of about 2 mm. 11 cuts are made parallel to each side to form a gobang, and a cellophane (registered trademark) adhesive tape is applied to the surface, and the gobang eye coating surface after the tape is peeled off is evaluated according to the following criteria. did: SA shows no peeling of the coating film. A shows a slight peeling of the coating film on the knife wound. B shows 1 to 20 pieces of all 100 gobangs. C is 21 or more of all the 100 gobangs peeled off.
  • Production Examples B1 to B10 Acrylic resin no. Production of B1 to B10 solutions Acrylic resins No. 1 produced in the above production examples A1 to A10. Each of A1 to A10 is an acrylic resin no. Used as B1 to B10.
  • pigment dispersion pastes B11 to B27 Production of B1 to B17 Pigment dispersion paste Nos. Produced in Examples A1 to A11 described above.
  • A1 to A11 are pigment dispersion paste Nos. Used as B1 to B17.
  • the average particle size of the above (Note 14) and (Note 15) is the volume-based particle size distribution measured by a laser diffraction scattering method using a microtrack particle size distribution measuring device (trade name “MT3300”, manufactured by Nikkiso Co., Ltd.). It is the value of the median diameter (d50).
  • Paint stability Each paint composition was sealed in a 100 mL glass wide-mouth bottle, stored in a constant temperature bath at 40 ° C. for 1 month, opened and investigated, and the paint settled and phase separated. Were assessed and evaluated according to the following criteria: SA is good with no problem. A is settled with paint, but the settling state is resolved by stirring for 5 minutes or less.
  • B is slightly affected by sedimentation and / or phase separation of paint for 5 minutes.
  • the settling state or phase separation is resolved by stirring for 60 minutes or less over C. At least one of the settling and phase separation of the paint is remarkable, and even if stirring is performed for more than 60 minutes, the settling state or phase separation is not solved.
  • Comparative production examples B20 and B21 B30-No. Production Example of B31 A coating composition No. B31 was prepared in the same manner as in Comparative Production Example B19 except that the content of blending shown in Table 11 was used. B30, coating composition No. B31 was obtained.
  • Tables 612 to 15 show the results of the tests performed on the coating compositions according to the test conditions described later.
  • test plate B31 was vertically coated so as to have a dry film thickness of 12 ⁇ m, and baked at 150 ° C. for 20 minutes to obtain “test plate B”.
  • test plate B the sagging state of the coating film was evaluated around the punch hole.
  • the coating conditions at this time were a temperature of 25 ° C. and a relative humidity of 80%: A is good without sagging of the coating film B is 1mm around the punch hole.
  • For C the sagging of the coating film is found 2 mm or more around the punch hole
  • test plate C The adhesion, weather resistance, and design properties of the test plate C were evaluated according to the descriptions in (Note 22) to (Note 24) described above.

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Abstract

Le problème que la présente invention se propose de résoudre est de proposer une pâte de dispersion de pigment qui a une excellente stabilité au stockage et une composition de revêtement qui a une adhésion satisfaisante à des matériaux de base et a l'excellente aptitude à cacher les matériaux de base. L'invention concerne une pâte de dispersion de pigment qui comprend une résine (a) pour disperser des pigments, un pigment d'aluminium (b) ayant un diamètre moyen de particule de 20-150 nm et un rapport d'allongement moyen de 7 ou moins, et un solvant organique, caractérisé par le fait que le pigment d'aluminium (b) est contenu dans une quantité de 5-100 parties en masse pour 100 parties en masse sur une base solide de la résine (a) pour disperser des pigments et qu'un film de revêtement sec d'une épaisseur de 6 µm obtenu par application de la pâte de dispersion de pigment a une transmittance de la lumière à toute longueur d'onde dans la plage de 300-700 nm de 0,1 % ou moins.
PCT/JP2012/074277 2011-09-29 2012-09-21 Pâte de dispersion de pigment, composition de revêtement, procédé de formation d'un film de revêtement et article revêtu WO2013047385A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011214800A JP2014237731A (ja) 2011-09-29 2011-09-29 顔料分散ペースト及び塗料組成物
JP2011-214800 2011-09-29
JP2011287406A JP2014237067A (ja) 2011-12-28 2011-12-28 塗膜形成方法及び塗装物品
JP2011-287406 2011-12-28

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WO2014196650A1 (fr) * 2013-06-07 2014-12-11 日産化学工業株式会社 Matériau comprenant un complexe ionique ayant pour fonction d'empêcher l'adhérence de matière biologique, et procédé de fabrication
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CN112552769A (zh) * 2013-06-07 2021-03-26 日产化学工业株式会社 具有抑制生物物质附着的能力的离子络合材料及其制造方法
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KR20160136302A (ko) * 2014-03-28 2016-11-29 도요 알루미늄 가부시키가이샤 플레이크상 금속 안료, 및 플레이크상 금속 안료의 제조 방법
JPWO2015146977A1 (ja) * 2014-03-28 2017-04-13 東洋アルミニウム株式会社 フレーク状金属顔料、それを含むメタリック組成物および塗布物、ならびにフレーク状金属顔料の製造方法
US10293406B2 (en) 2014-03-28 2019-05-21 Toyo Aluminium Kabushiki Kaisha Flaky metal pigment and method of manufacturing flaky metal pigment
KR102381106B1 (ko) * 2014-03-28 2022-03-30 도요 알루미늄 가부시키가이샤 플레이크상 금속 안료, 및 플레이크상 금속 안료의 제조 방법

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