Classifications

• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
• • 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
• • 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
• • 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
• • 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
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • 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
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to a photoluminescent pigment dispersion, a photoluminescent coating composition, and a method for forming a multilayer coating film.
• VOCs volatile organic compounds
• VOCs volatile organic compounds
• the coating film formed by painting the object is expected to protect the object being painted and also to give it a design (beautiful appearance), and metallic paint colors in particular are popular as they exude a sense of luxury.
• Patent Document 1 describes an aluminum pigment composition for water-based paints that contains at least an aluminum pigment, a rheology control agent, and an organic solvent, in which the organic solvent has a solubility parameter of 6 to 12 and a solubility in water at 20°C of 30% by mass or less, and the rheology control agent is added in an amount of 2.5 parts by mass per 100 parts by mass of solids in a resin emulsion and the viscosity is measured using a B-type viscometer, the viscosity B60 at 60 revolutions and the viscosity B6 at 6 revolutions are both in the range of 0.3 to 30 Pa ⁇ s, and the thixotropic index B6/B60, which is the ratio of B6 to B60, is 1 to 60.
• This aluminum pigment composition for water-based paints is characterized in that the orientation of the aluminum pigment after application is improved, improving metallic unevenness, and thus achieving a color tone and appearance comparable to that of organic solvent-based paints.
• the above aluminum pigment composition for water-based paints has good luster, but in recent years, there has been a demand for further reductions in the amount of volatile organic compounds (VOCs).
• VOCs volatile organic compounds
• the present invention aims to provide a glittering pigment dispersion that can be used to manufacture a glittering paint composition that has a low content of volatile organic compounds (VOCs) and can form a coating film with excellent glittering properties.
• VOCs volatile organic compounds
• the present invention provides a photoluminescent pigment dispersion, a photoluminescent coating composition, and a method for forming a multilayer coating film, which include the following aspects:
• a brilliant pigment dispersion comprising a silica-treated aluminum pigment (A) having an amino group on its surface, a first dispersing resin (B), and water,
• the solid content of the silica-treated aluminum pigment (A) having an amino group on its surface is 90 mass% or more
• the first dispersion resin (B) is a polymer of a composition containing a polymerizable unsaturated monomer (b1) having an acidic functional group, a nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and another polymerizable unsaturated monomer (b3),
• a brilliant pigment dispersion, the content of water being 90 mass % or more based on the amount of the solvent in the brilliant pigment dispersion.
• Item 2 The glittering pigment dispersion according to Item 1, wherein the silica-treated aluminum pigment (A) having an amino group on its surface includes a silica-treated aluminum pigment (A1) having an amino group and an alkyl group on its surface.
• Item 3 The photoluminescent pigment dispersion according to item 1 or 2, wherein the polymerizable unsaturated monomer (b1) containing an acidic functional group includes a polymerizable unsaturated monomer containing a carboxyl group.
• Item 4 The photoluminescent pigment dispersion according to any one of items 1 to 3, further comprising a second dispersing resin (C) which is a polymer of a composition containing a polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of a tertiary amino group and a quaternary ammonium base, a nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and another polymerizable unsaturated monomer (c3).
• a second dispersing resin (C) which is a polymer of a composition containing a polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of a tertiary amino group and a quaternary ammonium base, a nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and another polymerizable unsaturated monomer (c3).
• Step (1) A step of applying a colored coating composition (X) onto a substrate to form a colored coating film
• Step (2) A step of applying the glittering coating composition (Y) described in item 5 onto the colored coating film obtained in step (1) to form a glittering coating film
• Step (3) A step of applying a clear coating composition (Z) onto the glossy coating film obtained in step (2) to form a clear coating film
• the photoluminescent pigment dispersion of the present invention it is possible to produce a photoluminescent coating composition that contains a small amount of volatile organic compounds (VOCs) and can form a coating film with excellent photoluminescence.
• VOCs volatile organic compounds
• the term "comprise” is a concept that encompasses “consist essentially of” and “consist only of.”
• the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range.
• the upper or lower limit of a numerical range described in this specification, including the claims may be replaced with the upper or lower limit shown in the examples or a value that can be unambiguously derived from the examples.
• a numerical value connected with " ⁇ ” means a numerical range that includes the numerical values before and after " ⁇ " as the lower and upper limits.
• the photoluminescent pigment dispersion of the present invention will be described in more detail below.
• the brilliant pigment dispersion of the present invention is a brilliant pigment dispersion containing a silica-treated aluminum pigment (A) having an amino group on its surface, a first dispersing resin (B), and water,
• the solid content of the silica-treated aluminum pigment (A) having an amino group on its surface is 90 mass% or more
• the first dispersion resin (B) is a polymer of a composition containing a polymerizable unsaturated monomer (b1) having an acidic functional group, a nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and another polymerizable unsaturated monomer (b3),
• the content of water in the brilliant pigment dispersion is 90 mass % or more based on the amount of the solvent in the brilliant pigment dispersion.
• the water content is preferably 92 mass% or more, and more preferably 94 mass% or more, based on the amount of solvent in the glittering pigment dispersion.
• the solvent include water and organic solvents.
• the amount of solvent in the glittering pigment dispersion is the total amount of one or more solvents contained in the glittering pigment dispersion.
• Silica-treated aluminum pigment having amino groups on its surface has a solid content of 90% by mass or more.
• the solid content is preferably 95% by mass or more, and more preferably 99% by mass or more.
• the silica-treated aluminum pigment (A) having amino groups on its surface can be produced by reacting an aluminum pigment whose surface has been silica-treated with a silane coupling agent. Such modification of silica-treated aluminum pigments with amino groups is well known.
• the silica-treated aluminum pigment (A) having amino groups on its surface interacts with the acidic functional groups of the first dispersing resin (B) because of the amino groups on its surface. This improves the dispersibility of the silica-treated aluminum pigment (A), and the glossy coating composition containing the silica-treated aluminum pigment (A) can form a coating film with excellent glossiness.
• the average particle size of the silica-treated aluminum pigment (A) is preferably within the range of 1 to 100 ⁇ m, more preferably within the range of 5 to 50 ⁇ m, and even more preferably within the range of 7 to 30 ⁇ m.
• the thickness is preferably within the range of 0.01 to 1.0 ⁇ m, and even more preferably within the range of 0.02 to 0.5 ⁇ m.
• the silica-treated aluminum pigment (A) having amino groups on its surface preferably includes a silica-treated aluminum pigment (A1) having amino groups and alkyl groups on its surface, from the viewpoints of dispersibility and the water resistance and luster of the coating film formed.
• the silica-treated aluminum pigment (A1) having amino and alkyl groups on its surface can be produced by reacting an aluminum pigment having a silica-treated surface with a silane coupling agent. Such modification of silica-treated aluminum pigments with amino and alkyl groups is well known.
• the content of the silica-treated aluminum pigment (A) having amino groups on its surface in the brilliant pigment dispersion of the present invention is preferably 60 to 95 parts by mass, more preferably 65 to 93 parts by mass, and even more preferably 70 to 90 parts by mass, based on 100 parts by mass of the solid content in the brilliant pigment dispersion, from the viewpoint of producing a brilliant coating composition that has a low content of volatile organic compounds (VOCs) and can form a coating film with excellent brilliant properties.
• VOCs volatile organic compounds
• the first dispersion resin (B) is a polymer of a composition containing a polymerizable unsaturated monomer (b1) containing an acidic functional group, a nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and other polymerizable unsaturated monomers (b3).
• Examples of the polymerizable unsaturated monomer (b1) containing an acidic functional group include polymerizable unsaturated monomers containing a carboxyl group, polymerizable unsaturated monomers containing a phosphoric acid group, and polymerizable unsaturated monomers containing a sulfonic acid group, and among these, it is preferable to include a polymerizable unsaturated monomer containing a carboxyl group.
• the above-mentioned polymerizable unsaturated monomers containing a carboxyl group are compounds having one or more carboxyl groups and one polymerizable unsaturated group in one molecule, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and maleic anhydride. These can be used alone or in combination of two or more.
• the polymerizable unsaturated monomer having a phosphoric acid group is a compound having one or more phosphoric acid groups and one polymerizable unsaturated group in one molecule, and examples thereof include acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypoly(oxyethylene)glycol (meth)acrylate, and acid phosphooxypoly(oxypropylene)glycol (meth)acrylate. These can be used alone or in combination of two or more.
• the polymerizable unsaturated monomer containing a sulfonic acid group is a compound having one or more sulfonic acid groups and one polymerizable unsaturated group in one molecule, and examples thereof include 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc.; sodium salts and ammonium salts of these sulfonic acids. These can be used alone or in combination of two or more.
• a polymerizable unsaturated group refers to an unsaturated group that can undergo radical polymerization.
• examples of such polymerizable unsaturated groups include vinyl groups and (meth)acryloyl groups.
• (meth)acrylate means acrylate or methacrylate.
• (meth)acrylic acid means acrylic acid or methacrylic acid.
• (meth)acryloyl means acryloyl or methacryloyl.
• (meth)acrylamide means acrylamide or methacrylamide.
• the proportion of the polymerizable unsaturated monomer (b1) containing an acidic functional group in the monomers constituting the first dispersion resin (B) is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the polymerizable unsaturated monomer (b1) containing an acidic functional group, the nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (b3).
• the nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain is a monomer having a polyoxyalkylene chain and a polymerizable unsaturated group in one molecule.
• Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, and a block chain of polyoxyethylene and polyoxypropylene.
• the molecular weight of the polyoxyalkylene chain is preferably in the range of 150 to 3000, and more preferably in the range of 300 to 2500.
• nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain examples include, for example, tetraethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, n-butoxytetraethylene glycol (meth)acrylate, tetrapropylene glycol (meth)acrylate, methoxytetrapropylene glycol (meth)acrylate, ethoxytetrapropylene glycol (meth)acrylate, n-butoxytetrapropylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, etc., which can be used alone or in combination of two or more.
• the proportion of the nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain in the monomers constituting the first dispersion resin (B) is preferably 50 to 95% by mass, more preferably 55 to 93% by mass, and even more preferably 60 to 90% by mass, based on the total amount of the polymerizable unsaturated monomer (b1) containing an acidic functional group, the nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (b3).
• the other polymerizable unsaturated monomer (b3) is a compound having one polymerizable unsaturated bond in one molecule other than the above monomers (b1) and (b2), and specific examples thereof are listed below.
• Alkyl or cycloalkyl (meth)acrylates for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl
• Nitrogen-containing polymerizable unsaturated monomers (meth)acrylonitrile, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, adducts of glycidyl (meth)acrylate and amine compounds, and the like.
• (xi) Polymerizable unsaturated monomers having two or more polymerizable unsaturated groups in one molecule: allyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc.
• Epoxy group-containing polymerizable unsaturated monomers glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether, and the like.
• (xiii) Polymerizable unsaturated monomers having an ultraviolet absorbing functional group: 2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, and the like.
• Light-stable polymerizable unsaturated monomers 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like.
• (xv) Polymerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), and the like.
• (xvi) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
• (xvii) Hydroxyl group-containing polymerizable unsaturated monomers monoesters of polyhydric alcohols and (meth)acrylic acid (other than the above-mentioned nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain), such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; compounds obtained by ring-opening polymerization of the above-mentioned monoesters of polyhydric alcohols and (meth)acrylic acid with ⁇ -caprolactone, and the like.
• the proportion of the other polymerizable unsaturated monomer (b3) in the monomers constituting the first dispersion resin (B) is preferably 1 to 25 mass%, more preferably 2 to 15 mass%, and even more preferably 3 to 10 mass%, based on the total amount of the polymerizable unsaturated monomer (b1) containing an acidic functional group, the nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (b3).
• the polymerization of the monomers constituting the first dispersion resin (B) can be carried out by known methods, such as solution polymerization in an organic solvent or emulsion polymerization in water, with solution polymerization being particularly preferred.
• An example of a polymerization method using a solution polymerization method is a method in which a mixture of a polymerizable unsaturated monomer (b1) containing an acidic functional group, a nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain, and other polymerizable unsaturated monomers (b3) and a radical polymerization initiator is dissolved or dispersed in an organic solvent, and then heated and stirred at a temperature of about 80°C to about 200°C for about 1 to 10 hours to polymerize the mixture.
• organic solvents examples include hydrocarbon solvents such as heptane, toluene, xylene, octane, and mineral spirits; 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, and cyclohexanone; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, and isobutanol; ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether,
• the radical polymerization initiator may, for example, be ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, or methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, or n-butyl-4,4-bis(tert-butylperoxy)valerate; hydroperoxides such as cumene hydroperoxide or 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, diisopropylbenzene peroxide, or tert- Examples of the
• the first dispersion resin (B) preferably has a hydroxyl value in the range of 0.1 to 20 mgKOH/g, more preferably in the range of 0.5 to 15 mgKOH/g, and even more preferably in the range of 1 to 10 mgKOH/g.
• the acid value of the first dispersing resin (B) is preferably within the range of 5 to 200 mg KOH/g, more preferably within the range of 15 to 180 mg KOH/g, and even more preferably within the range of 30 to 150 mg KOH/g.
• the weight average molecular weight of the first dispersing resin (B) is preferably within the range of 1,000 to 50,000, more preferably within the range of 2,000 to 40,000, and even more preferably within the range of 3,000 to 30,000.
• the content of the first dispersion resin (B) in the photochromic pigment dispersion of the present invention is preferably 0.1 to 20.0 parts by mass, more preferably 0.2 to 15.0 parts by mass, and even more preferably 0.3 to 10.0 parts by mass, based on 100 parts by mass of the solid content in the photochromic pigment dispersion.
• the photoluminescent pigment dispersion of the present invention preferably further contains a second dispersing resin (C) from the viewpoint of producing a photoluminescent coating composition that has a low content of volatile organic compounds (VOCs) and can form a coating film with excellent photoluminescence.
• C second dispersing resin
• the second dispersing resin (C) is a polymer of a composition containing a polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of a tertiary amino group and a quaternary ammonium base, a nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and another polymerizable unsaturated monomer (c3).
• a dispersing resin corresponds to both the first dispersing resin (B) and the second dispersing resin (C), it is considered to be included in the first dispersing resin (B).
• polymerizable unsaturated monomers containing a tertiary amino group examples include N,N-dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-di-t-butylaminoethyl (meth)acrylate, and N,N-dimethylaminobutyl (meth)acrylate; and N,N-dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, and N,N-dimethylaminopropyl (meth)acrylamide.
• examples of quaternary ammonium base-containing polymerizable unsaturated monomers include (meth)acryloyloxyalkyltrialkylammonium salts such as 2-(methacryloyloxy)ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, and 2-(methacryloyloxy)ethyltrimethylammonium dimethylphosphate; and (meth)acryloylaminoalkyltrialkylammonium salts such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide.
• (meth)acryloyloxyalkyltrialkylammonium salts such as 2-(methacryloyloxy)ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, and 2-(meth
• the polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of a tertiary amino group and a quaternary ammonium base preferably contains a polymerizable unsaturated monomer containing a tertiary amino group, from the viewpoint of producing a glittering coating composition that has a low content of volatile organic compounds (VOCs) and can form a coating film with excellent glittering properties.
• VOCs volatile organic compounds
• the proportion of the polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of the tertiary amino group and the quaternary ammonium base in the monomers constituting the second dispersion resin (C) is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and even more preferably 1 to 10 mass%, based on the total amount of the polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of the tertiary amino group and the quaternary ammonium base, the nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (c3).
• nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain (c2) the compounds described in the description of the nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain (b2) can be used.
• the proportion of the nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain in the monomers constituting the second dispersion resin (C) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total amount of the polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of tertiary amino groups and quaternary ammonium bases, the nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (c3).
• the other polymerizable unsaturated monomer (c3) is a compound having one polymerizable unsaturated bond in one molecule other than the above monomers (c1) and (c2), and specific examples thereof are listed below.
• Alkyl or cycloalkyl (meth)acrylates for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl
• (x) Carboxyl group-containing polymerizable unsaturated monomers (meth)acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl (meth)acrylate, etc.
• Hydroxyl group-containing polymerizable unsaturated monomers monoesters of polyhydric alcohols and (meth)acrylic acid (other than the above-mentioned nonionic polymerizable unsaturated monomer (b2) having a polyoxyalkylene chain), such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; compounds obtained by ring-opening polymerization of the above-mentioned monoesters of polyhydric alcohols and (meth)acrylic acid with ⁇ -caprolactone, and the like.
• (xii) Polymerizable unsaturated monomers having two or more polymerizable unsaturated groups in one molecule: allyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc.
• Epoxy group-containing polymerizable unsaturated monomers glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether, and the like.
• (xvii) Light-stable polymerizable unsaturated monomers 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like.
• (xviii) Polymerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), and the like.
• (xix) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride, etc.
• the proportion of the other polymerizable unsaturated monomer (c3) in the monomers constituting the second dispersion resin (C) is preferably 45 to 90% by mass, more preferably 55 to 87% by mass, and even more preferably 65 to 85% by mass, based on the total amount of the polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of tertiary amino groups and quaternary ammonium bases, the nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain, and the other polymerizable unsaturated monomer (c3).
• the monomers constituting the second dispersion resin (C) can be polymerized by a conventionally known method.
• the second dispersion resin (C) is preferably an AB block polymer that can be obtained by an addition-fragmentation chain transfer polymerization method using an addition-fragmentation chain transfer agent.
• a block polymer can be produced by addition-fragmentation chain transfer polymerization of the monomer components constituting the block in the presence of the addition-fragmentation chain transfer agent.
• the addition-fragmentation chain transfer polymerization can be carried out, for example, by a solution polymerization method in an organic solvent or an emulsion polymerization method in water.
• a known radical polymerization initiator can be used in combination with the addition-fragmentation chain transfer agent as needed.
• addition-fragmentation chain transfer agent for example, 2,4-diphenyl-4-methyl-1-pentene (sometimes abbreviated as " ⁇ -methylstyrene dimer” or “MSD”) can be suitably used.
• MSD is preferably used in the first polymerization.
• the AB block polymer preferably comprises an A block containing a polymerizable unsaturated monomer (c1) containing at least one functional group selected from the group consisting of the tertiary amino group and the quaternary ammonium base and another polymerizable unsaturated monomer (c3), and a B block containing a nonionic polymerizable unsaturated monomer (c2) having a polyoxyalkylene chain and another polymerizable unsaturated monomer (c3).
• the ratio (mass ratio) of the total amount of monomers constituting the A block to the total amount of monomers constituting the B block is preferably 10/90 to 60/40, and more preferably within the range of 20/80 to 50/50, from the viewpoint of the dispersibility of the silica-treated aluminum pigment (A) having amino groups on its surface.
• the second dispersion resin (C) preferably has a hydroxyl value in the range of 10 to 100 mgKOH/g, more preferably in the range of 20 to 80 mgKOH/g, and even more preferably in the range of 30 to 60 mgKOH/g.
• the second dispersing resin (C) preferably has an amine value in the range of 1 to 30 mg KOH/g, more preferably in the range of 3 to 25 mg KOH/g, and even more preferably in the range of 5 to 20 mg KOH/g.
• the weight average molecular weight of the second dispersing resin (C) is preferably within the range of 1,000 to 50,000, more preferably within the range of 2,000 to 40,000, and even more preferably within the range of 3,000 to 30,000.
• the content of the second dispersion resin (C) in the photochromic pigment dispersion of the present invention is preferably 1 to 25 parts by mass, more preferably 3 to 23 parts by mass, and even more preferably 5 to 20 parts by mass, based on 100 parts by mass of the solid content in the photochromic pigment dispersion.
• the brilliant pigment dispersion of the present invention may further contain, as necessary, an organic solvent, a pigment other than the silica-treated aluminum pigment (A) having amino groups on its surface, a viscosity adjuster, an anti-settling agent, an ultraviolet absorber, a light stabilizer, and the like.
• the solids content of the photoluminescent pigment dispersion of the present invention is preferably within the range of 10 to 50 mass %, and more preferably within the range of 20 to 40 mass %, from the viewpoint of producing a photoluminescent coating composition that has a low content of volatile organic compounds (VOCs) and can form a coating film with excellent photoluminescence.
• VOCs volatile organic compounds
• the glittering coating composition (Y) of the present invention is a glittering coating composition containing the glittering pigment dispersion of the present invention and a film-forming resin.
• the water content in the glittering coating composition (Y) of the present invention is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 85 mass% or more, based on the amount of solvent in the glittering coating composition (Y).
• the solvent include water and organic solvents.
• the amount of solvent in the glittering coating composition (Y) is the total amount of one or more solvents contained in the glittering coating composition (Y).
• film-forming resin examples include acrylic resin, polyester resin, epoxy resin, urethane resin, etc.
• acrylic resin examples include ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, (meth)acrylic acid esters having functional groups such as hydroxyl groups, amide groups, methylol groups, and epoxy groups, and resins obtained by copolymerizing other (meth)acrylic acid esters, styrene, etc.
• polyester resins obtained by a condensation reaction between a polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, trimethylolpropane, or pentaerythritol and a polycarboxylic acid component such as adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride, hexahydrophthalic anhydride, or trimellitic anhydride can be used.
• a polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, trimethylolpropane, or pentaerythritol
• a polycarboxylic acid component such as adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride, hexahydrophthalic anhydride, or trimellitic anhydride
• epoxy resin is the so-called bisphenol A type epoxy resin, which is produced by a condensation reaction between bisphenol A and epichlorohydrin.
• urethane resin examples include compounds obtained by an addition reaction between a diisocyanate compound and a polyhydric alcohol, and those obtained by reacting the above-mentioned acrylic resin, polyester resin, or epoxy resin with a diisocyanate compound to increase the molecular weight.
• the film-forming resin preferably has a sufficient amount of hydrophilic groups to be water-soluble or water-dispersible.
• hydrophilic group examples include a carboxyl group, a hydroxyl group, a methylol group, an amino group, a sulfonic acid group, and a polyoxyethylene bond, and among these, a carboxyl group is preferable.
• hydrophilic groups are preferably neutralized with sodium hydroxide, an amine compound, or the like to form an alkaline salt.
• the above resin can also be dispersed in water by emulsion polymerization of the polymerizable component in the presence of a surfactant or a water-soluble resin. Furthermore, the resin can also be dispersed in water in the presence of an emulsifier, for example. In this case, the base resin does not need to contain the hydrophilic group.
• the above-mentioned film-forming resins may be used alone or in combination of two or more kinds.
• the content of the film-forming resin in the glittering coating composition (Y) of the present invention is preferably within the range of 30 to 85 parts by mass, more preferably within the range of 35 to 80 parts by mass, based on 100 parts by mass of the total solids in the glittering coating composition (Y).
• the bright coating composition (Y) of the present invention preferably further contains a curing agent.
• the above-mentioned curing agents include, for example, amino resins, polyisocyanate compounds, blocked polyisocyanate compounds, etc.
• the curing agents can be used alone or in combination of two or more kinds.
• the content ratio of the film-forming resin and the curing agent is preferably within the range of 50 to 90 mass %, particularly preferably 60 to 85 mass %, and the content ratio of the latter is preferably within the range of 10 to 50 mass %, particularly preferably 15 to 40 mass %, based on the total mass of both components.
• the photoluminescent coating composition (Y) of the present invention may contain, as desired, a color pigment, an extender pigment, a photoluminescent pigment other than the silica-treated aluminum pigment (A) having an amino group on its surface, a curing catalyst, an ultraviolet absorber, an antifoaming agent, a viscosity adjuster, a surface conditioner, an organic solvent, etc.
• color pigments examples include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, threne pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, etc., and among these, carbon black is preferred.
• the content of the coloring pigment is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the resin solids in the glittering coating composition (Y).
• extender pigment examples include barium sulfate, talc, clay, kaolin, barium carbonate, calcium carbonate, silica, alumina white, etc.
• the content of the extender pigment is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the resin solids in the glittering paint composition (Y).
• Examples of the luster pigment other than the silica-treated aluminum pigment (A) having amino groups on its surface include aluminum (including vapor-deposited aluminum) other than the silica-treated aluminum pigment (A) having amino groups on its surface, copper, zinc, brass, nickel, glass flakes, aluminum oxide, mica, aluminum oxide coated with titanium oxide and/or iron oxide, mica coated with titanium oxide and/or iron oxide, etc.
• the content of the glittering pigment is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the resin solids in the glittering paint composition (Y).
• the curing catalyst may, for example, be tin octylate, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di(2-ethylhexanoate), dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid salts, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acids, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, or versatic acid.
• organometallic compounds such as smuth, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, and tetra(2-ethylhexyl)titanate
• sulfonic acid group-containing compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenesulfonic acid
• phosphate group-containing compounds such as monobutyl phosphate, dibutyl phosphate, mono 2-ethylhexyl phosphate, di 2-ethylhexyl phosphate, alkyl ether phosphate, polyoxyethylene alkyl ether phosphate, and phosphate group-containing resins.
• the glittering paint composition (Y) of the present invention When using the glittering paint composition (Y) of the present invention, it can be applied by diluting it with water and/or an organic solvent, etc., as necessary, and adjusting the viscosity to an appropriate level.
• the appropriate viscosity varies depending on the paint composition, but it is preferable to adjust the viscosity, for example, using water and/or an organic solvent so that it is within the range of 2000 to 7000 mPa ⁇ s when measured at 20°C and 6 rpm using a B-type viscometer.
• the coating solids concentration of the glittering paint composition (Y) is preferably 3 to 30 mass%, and more preferably about 5 to 25 mass%.
• the glittering coating composition (Y) of the present invention may be either a one-component coating or a multi-component coating, but it is preferable to use a one-component coating, as this eliminates the need for a coating mixing process, provides excellent productivity, and simplifies maintenance of coating machines.
• the glittering coating composition (Y) of the present invention can be applied to a substrate by a method known per se, such as air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, etc., and electrostatic application may be performed during coating. Of these, air spray coating, rotary atomization coating, etc. are preferred. Furthermore, such coating methods can be performed once or in several separate steps until the desired film thickness is obtained.
• the amount of application of the glittering coating composition (Y) of the present invention is preferably 0.5 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, and even more preferably 2 to 10 ⁇ m, in terms of the cured film thickness.
• the method for forming a multilayer coating film of the present invention comprises the following steps (1) to (4): Step (1): A step of applying a colored coating composition (X) onto a substrate to form a colored coating film; Step (2): A step of applying the glittering coating composition (Y) of the present invention onto the colored coating film obtained in step (1) to form a glittering coating film; Step (3): A step of applying a clear coating composition (Z) onto the glossy coating film obtained in step (2) to form a clear coating film; Step (4): A method for forming a multilayer coating film, comprising a step of simultaneously curing the multilayer coating film including the color coating film, the glossy coating film and the clear coating film formed in steps (1), (2) and (3), respectively, by heating the multilayer coating film.
• substrates are not particularly limited, and examples include the outer panels of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automobile parts; and the outer panels of household electrical appliances such as mobile phones and audio equipment. Of these, the outer panels of automobile bodies and automobile parts are preferred.
• the materials of these substrates are not particularly limited. Examples include metal materials such as iron, aluminum, brass, copper, tinplate, stainless steel, zinc-plated steel, and zinc alloy (Zn-Al, Zn-Ni, Zn-Fe, etc.)-plated steel; resins such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, and epoxy resin; plastic materials such as various FRPs; inorganic materials such as glass, cement, and concrete; wood; and fibrous materials such as paper and cloth. Of these, metal materials and plastic materials are preferred.
• metal materials such as iron, aluminum, brass, copper, tinplate, stainless steel, zinc-plated steel, and zinc alloy (Zn-Al, Zn-Ni, Zn-Fe, etc.)-plated steel
• resins such as polyethylene resin, polypropylene resin, acrylonitrile
• the surfaces of the objects to which the multi-layer coating film is applied may be metal surfaces such as the outer panels of automobile bodies, automobile parts, household electrical appliances, and the metal substrates such as the steel plates that make up these products, which have been subjected to surface treatments such as phosphate treatment, chromate treatment, and composite oxide treatment.
• a coating film may be further formed on an object that may or may not have been surface-treated.
• a surface treatment may be applied to the substrate to be coated as necessary, and a primer coating film and/or intermediate coating film may be formed thereon.
• the primer coating film and/or intermediate coating film may be formed using a known primer and/or intermediate coating composition that is commonly used in the painting of automobile bodies.
• an electrodeposition paint preferably a cationic electrodeposition paint
• an electrodeposition paint preferably a cationic electrodeposition paint
• a crosslinkable functional group such as a carboxyl group, a hydroxyl group, or the like
• an acrylic resin such as a polyester resin, an alkyd resin, a urethane resin, or an epoxy resin
• an amino resin such as a melamine resin or a urea resin
• a crosslinking agent such as an optionally blocked polyisocyan
• thermosetting colored coating composition known for use in painting automobile bodies and the like can be used.
• a thermosetting coating composition containing a base resin having a crosslinkable functional group, a crosslinking agent, a color pigment, and an extender pigment can be suitably used.
• a luster pigment can also be included.
• crosslinkable functional groups contained in the base resin include carboxyl groups, hydroxyl groups, and epoxy groups.
• Examples of the base resin include acrylic resin, polyester resin, alkyd resin, and urethane resin.
• crosslinking agent examples include melamine resins, polyisocyanate compounds, and blocked polyisocyanate compounds.
• the colored coating composition (X) either an aqueous coating composition or an organic solvent-based coating composition may be used, but from the viewpoint of reducing the environmental load, etc., an aqueous coating composition is preferred.
• the method of applying the colored coating composition (X) is not particularly limited, but a wet coating film can be formed by, for example, air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, or other coating methods. In these coating methods, electrostatic application may be performed as necessary. Of these, air spray coating or rotary atomization coating is particularly preferred.
• the amount of colored coating composition (X) applied is preferably an amount that results in a cured film thickness of 5 to 30 ⁇ m, and more preferably an amount that results in a cured film thickness of 7 to 20 ⁇ m.
• the viscosity of the colored coating composition (X) is adjusted appropriately using a solvent such as water or an organic solvent so that the viscosity is within a range suitable for the coating, preferably within a range of about 15 to 60 seconds at 20°C, and particularly preferably within a range of about 20 to 50 seconds, as measured using a Ford Cup No. 4 viscometer.
• thermosetting clear coating composition for coating automobile bodies and the like
• any known thermosetting clear coating composition for coating automobile bodies and the like can be used, such as an organic solvent-based thermosetting coating composition containing a base resin having a crosslinkable functional group and a curing agent, an aqueous thermosetting coating composition, a powder thermosetting coating composition, etc.
• Examples of the crosslinkable functional groups possessed by the base resin include carboxyl groups, hydroxyl groups, epoxy groups, and silanol groups.
• Examples of the types of base resin include acrylic resins, polyester resins, alkyd resins, urethane resins, epoxy resins, and fluororesins.
• Examples of the curing agent include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins, carboxyl group-containing compounds, carboxyl group-containing resins, epoxy group-containing resins, and epoxy group-containing compounds.
• Preferred combinations of base resin/curing agent for the clear coating composition (Z) include carboxyl group-containing resin/epoxy group-containing resin, hydroxyl group-containing resin/polyisocyanate compound, hydroxyl group-containing resin/blocked polyisocyanate compound, hydroxyl group-containing resin/melamine resin, etc.
• the clear paint composition (Z) may be a one-component paint or a multi-component paint such as a two-component urethane resin paint.
• the clear coating composition (Z) may contain color pigments, luster pigments, dyes, etc., as needed, to the extent that transparency is not impaired, and may further contain extender pigments, ultraviolet absorbers, light stabilizers, defoamers, thickeners, rust inhibitors, surface conditioners, etc., as appropriate.
• the method of applying the clear coating composition (Z) is not particularly limited, but a wet coating film can be formed by, for example, air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, or other coating methods. In these coating methods, electrostatic application may be performed as necessary. Of these, air spray coating or rotary atomization coating is particularly preferred.
• the amount of clear coating composition (Z) applied is preferably an amount that results in a cured film thickness of 10 to 50 ⁇ m, and more preferably an amount that results in a cured film thickness of 20 to 40 ⁇ m.
• the viscosity of the clear coating composition (Z) is adjusted appropriately using a solvent such as an organic solvent so that the viscosity is within a range suitable for such coating, preferably within a range of about 15 to 60 seconds, and particularly preferably within a range of about 20 to 50 seconds, at 20°C, as measured using a Ford Cup No. 4 viscometer.
• the heating can be performed by known means, for example, a drying oven such as a hot air oven, an electric oven, or an infrared induction heating oven.
• the heating temperature is preferably within the range of 70 to 160°C, more preferably 90 to 150°C.
• the heating time is not particularly limited, but is preferably within the range of 10 to 60 minutes, more preferably 20 to 40 minutes.
• the resulting electrocoated surface of the steel plate was then coated with "WP-523H" (product name: Kansai Paint Co., Ltd., acrylic-melamine resin-based water-based undercoat paint) using an air spray to a thickness of 20 ⁇ m based on the cured coating film, and after leaving it for 3 minutes, it was preheated at 80°C for 3 minutes to form an uncured undercoat coating film, completing the coating process.
• WP-523H product name: Kansai Paint Co., Ltd., acrylic-melamine resin-based water-based undercoat paint
• 1% of the total amount of the monomer emulsion described below and 5 parts of a 6% aqueous solution of ammonium persulfate were introduced into the reaction vessel and held at 80 ° C. for 15 minutes. Thereafter, the remaining monomer emulsion was dropped into the reaction vessel held at the same temperature over 3 hours, and after completion of the dropping, the mixture was aged for 1 hour, and then cooled to 30 ° C. while gradually adding 40 parts of a 5% aqueous solution of 2-(dimethylamino)ethanol to the reaction vessel, and the mixture was discharged while filtering through a 100-mesh nylon cloth, to obtain a hydroxyl-containing acrylic resin emulsion (1) with a solids concentration of 45%.
• the resulting hydroxyl-containing acrylic resin emulsion (1) had a hydroxyl value of 43 mgKOH/g and an acid value of 12 mgKOH/g.
• Monomer emulsion 50 parts of deionized water, 10 parts of styrene, 40 parts of methyl methacrylate, 35 parts of ethyl acrylate, 3.5 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 1.5 parts of acrylic acid, 1.0 part of "Aqualon KH-10" and 0.03 parts of ammonium persulfate were mixed and stirred to obtain a monomer emulsion.
• 59 parts of trimellitic anhydride was added to this reaction product, and an addition reaction was carried out at 170 ° C. for 30 minutes, after which the mixture was cooled to 50 ° C. or less, and 2- (dimethylamino) ethanol was added in an equivalent amount to the acid group to neutralize it, and then deionized water was gradually added to obtain a hydroxyl group-containing polyester resin (2) solution with a solid content concentration of 45% and a pH of 7.2.
• the resulting hydroxyl-containing polyester resin (2) had a hydroxyl value of 128 mgKOH/g, an acid value of 35 mgKOH/g and a weight average molecular weight of 13,000.
• the resulting first dispersion resin (B-1) had a weight average molecular weight of 5,000, an acid value of 78 mg KOH/g, and a hydroxyl value of 6.5 mg KOH/g.
• the weight average molecular weight of the obtained polymer A was about 3000.
• 41.7 parts of the macromonomer polymer A were charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping device, and the mixture was stirred and mixed in a nitrogen stream until the temperature reached 95°C.
• the following monomer mixture II and monomer mixture III were dropped over 3 hours, and the mixture was aged at 95°C for 30 minutes.
• carboxylic acid group-containing dispersion resin (3) had an acid value of 47 mg KOH/g, a hydroxyl value of 72 mg KOH/g, and a weight average molecular weight of 58,000.
• Phosphate group-containing polymerizable monomer 57.5 parts of monobutyl phosphate and 41 parts of isobutanol were placed in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping device, and the temperature was raised to 90°C. After that, 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours, and the mixture was further stirred and aged for 1 hour. After that, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution with a solid content of 50%. The acid value due to the phosphate group of the resulting monomer was 285 mgKOH/g.
• the resulting dispersion resin (5) containing a nonionic polymerizable unsaturated monomer having an amino group and a polyoxyalkylene chain had an amine value of 35.5 mgKOH/g, a hydroxyl value of 48.4 mgKOH/g and a number average molecular weight of 6,500.
• Production Example 1 of Glitter Pigment Dispersion In a stirring and mixing vessel, 30 parts (solids: 30 parts) of aluminum pigment A (a silica-treated aluminum pigment having amino groups and alkyl groups on the surface, average particle size (d50) 19 ⁇ m, average thickness 0.40 ⁇ m, solids concentration 100%), 80 parts of deionized water, and 2 parts (solids: 1.8 parts) of the first dispersion resin (B-1) obtained in Production Example 5 were uniformly mixed to obtain a glittering pigment dispersion (P-2).
• aluminum pigment A a silica-treated aluminum pigment having amino groups and alkyl groups on the surface, average particle size (d50) 19 ⁇ m, average thickness 0.40 ⁇ m, solids concentration 100%
• 80 parts of deionized water 80 parts
• 2 parts (solids: 1.8 parts) of the first dispersion resin (B-1) obtained in Production Example 5 were uniformly mixed to obtain a glittering pigment dispersion (P-2).
• the remaining monomer emulsion (1) was dropped into the reaction vessel held at the same temperature over a period of 3 hours, and aging was carried out for 1 hour after the end of the dropping.
• the monomer emulsion (2) described below was dropped over a period of 1 hour, and after aging for 1 hour, the reaction vessel was cooled to 30°C while gradually adding 40 parts of a 5% aqueous solution of dimethylethanolamine to the reaction vessel, and the mixture was discharged while filtering through a 100-mesh nylon cloth, to obtain a hydroxyl-containing acrylic resin emulsion (6) with a solids concentration of 30%.
• the resulting hydroxyl-containing acrylic resin emulsion (6) had a hydroxyl value of 25 mgKOH/g and an acid value of 33 mgKOH/g.
• Monomer emulsion (1) 42 parts of deionized water, 0.72 parts of "Aqualon KH-10", 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 parts of ethyl acrylate, and 21 parts of n-butyl acrylate were mixed and stirred to obtain monomer emulsion (1).
• Monomer emulsion (2) 18 parts of deionized water, 0.31 parts of "Aqualon KH-10", 0.03 parts of ammonium persulfate, 5.1 parts of methacrylic acid, 5.1 parts of 2-hydroxyethyl acrylate, 3 parts of styrene, 6 parts of methyl methacrylate, 1.8 parts of ethyl acrylate, and 9 parts of n-butyl acrylate were mixed and stirred to obtain monomer emulsion (2).
• the mixture was aged at 110°C for 30 minutes, and then an additional catalyst mixture consisting of 25 parts of ethylene glycol monobutyl ether and 0.5 parts of azobisisobutyronitrile was added dropwise over 1 hour.
• the mixture was then aged at 110°C for 1 hour and cooled to obtain a solution of acrylic resin (7) for dispersing color pigments with a solid content of 50%.
• the acrylic resin (7) for dispersing color pigments had a hydroxyl value of 43 mgKOH/g and a weight average molecular weight of about 20,000.
• a carboxyl group was added to the obtained condensation reaction product, 38.3 parts of trimellitic anhydride was further added, and the mixture was reacted at 170°C for 30 minutes, and then diluted with 2-ethyl-1-hexanol to obtain a hydroxyl group-containing polyester resin (8) solution having a solid content concentration of 70%.
• the obtained hydroxyl group-containing polyester resin (8) had a hydroxyl value of 150 mgKOH/g, an acid value of 46 mgKOH/g and a weight average molecular weight of 6,400.
• Example 11 of production of glittering coating composition (Y) 112 parts (31.8 parts solids) of the glittering pigment dispersion liquid (P-2) obtained in Example 1, 91 parts (13 parts solids) of the color pigment dispersion paste (P-16) obtained in Production Example 21, 83.3 parts (25 parts solids) of the hydroxyl-containing acrylic resin emulsion (6) obtained in Production Example 18, 35.7 parts (25 parts solids) of the hydroxyl-containing polyester resin (8) solution obtained in Production Example 20, 37.5 parts (30 parts solids) of "Cymel 325" (trade name, manufactured by Allnex Corporation, melamine resin, 80% solids), and 20.4 parts (10.2 parts solids) of the phosphate group-containing dispersion resin (4) solution obtained in Production Example 16 were uniformly mixed.
• a glittering coating composition (Y-1) having a pH of 7.8, a coating solids content of 14%, and a viscosity of 2000 mPa ⁇ s when measured at 20° C. and a rotation speed of 6 rpm using a B-type viscometer.
• the water content in the glittering coating composition (Y-1) was 89 mass% based on the amount of solvent in the glittering coating composition (Y).
• Example 22 The colored coating composition (X-1) obtained in Production Example 4 was electrostatically coated on the substrate prepared in "1. Preparation of substrate” above using a rotary atomizing bell-type coating machine to a cured film thickness of 12 ⁇ m, and then allowed to stand for 2 minutes to form a colored coating film. Furthermore, the glittering coating composition (Y-1) obtained in Example 11 was coated on the colored coating film using a robot bell manufactured by ABB Corporation under conditions of a booth temperature of 23°C and a humidity of 68% to a dry coating film thickness of 4 ⁇ m. The coating was allowed to stand for 3 minutes, and then preheated at 80°C for 3 minutes to form a glittering coating film.
• a clear coating composition (Z-1) "Magicron KINO-1210TW" (trade name, manufactured by Kansai Paint Co., Ltd., an acrylic resin-based organic solvent-based clear coating composition containing a carboxyl group-containing resin and an epoxy group-containing resin) was applied to form a dry coating film of 35 ⁇ m using a robot bell manufactured by ABB Co., Ltd. under conditions of a booth temperature of 23 ° C. and a humidity of 68% to form a clear coat coating film. After coating, it was left at room temperature for 7 minutes, and then heated at 140 ° C. for 30 minutes using a hot air circulation drying oven to simultaneously dry the multi-layer coating film to obtain a test plate.
• Brilliance grade Sg (15°) value A CCD chip was placed in the perpendicular direction to the planar direction of the measurement surface of each test plate to capture the image of the measurement surface.
• the CCD chip took an image of the measurement surface using light irradiated onto the measurement surface from an angle of 15° to the perpendicular direction, and the resulting images were analyzed with an image analysis algorithm that uses a histogram of brightness levels to evaluate the brilliance grade Sg (15°) value.
• a multi-angle colorimeter manufactured by BYK, product name: BYK-mac i
• the smaller the value the less grainy the texture. A value of 10 or less is considered a pass.
• test plates of Examples 22-32 passed both the brilliance grade Sg value and FF value, and the multi-layer coating film had excellent brilliance.
• test plates of Comparative Examples 9 and 10 failed the brilliance grade Sg value
• Comparative Examples 11 and 12 failed the FF value.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92146666

Family Applications (1)

Country Status (3)

Citations (5)

• 2024
  • 2024-01-31 WO PCT/JP2024/002963 patent/WO2024162367A1/ja not_active Ceased
  • 2024-01-31 CN CN202480004608.3A patent/CN120051539A/zh active Pending
  • 2024-01-31 JP JP2024542236A patent/JP7661631B2/ja active Active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events