WO2012033079A1 - Copolymère, composition de revêtement à base aqueuse le contenant et procédé de formation d'un film de revêtement multicouches - Google Patents

Copolymère, composition de revêtement à base aqueuse le contenant et procédé de formation d'un film de revêtement multicouches Download PDF

Info

Publication number
WO2012033079A1
WO2012033079A1 PCT/JP2011/070229 JP2011070229W WO2012033079A1 WO 2012033079 A1 WO2012033079 A1 WO 2012033079A1 JP 2011070229 W JP2011070229 W JP 2011070229W WO 2012033079 A1 WO2012033079 A1 WO 2012033079A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerizable unsaturated
unsaturated monomer
meth
group
acrylate
Prior art date
Application number
PCT/JP2011/070229
Other languages
English (en)
Japanese (ja)
Inventor
剛士 坪内
芳明 千野
藤井　毅
Original Assignee
関西ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 WO2012033079A1 publication Critical patent/WO2012033079A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • 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
    • B05D7/50—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas

Definitions

  • the present invention relates to a copolymer and a viscosity modifier comprising the copolymer. More specifically, the present invention relates to a copolymer that can be suitably used as a viscosity adjusting agent capable of developing a viscosity in an aqueous coating composition containing a coating additive, particularly a surfactant. The present invention also relates to an aqueous coating composition containing the copolymer and a method for forming a multilayer coating film using the aqueous coating composition.
  • a coating method for coating an object requiring an excellent appearance such as an automobile is performed by atomizing a paint from the viewpoint of the appearance and production efficiency of a formed coating film.
  • Specific examples of such a coating method include spray coating and rotary atomization coating.
  • the paint used is generally low in viscosity when spraying, rotating atomization, etc., and the smaller paint particles are formed, which makes smoothness smooth. It is preferable because an excellent coating film is formed.
  • the viscosity of the paint is high, and it is difficult for the paint layer to be mixed with the paint to be applied on the upper layer, and a coating film with excellent sharpness is formed. ,preferable.
  • the paint contains a bright pigment such as an aluminum pigment, if the paint viscosity is high after the paint is applied to an object, the bright pigment in the paint is difficult to move and the orientation is not easily disturbed.
  • a coating film excellent in glitter generally has a remarkable change in brightness due to the observation angle when the coating film is observed at different angles, and the glitter pigment is relatively contained in the coating film.
  • the paint is excellent in that the viscosity is low when the shear rate is large as in atomization and the viscosity is high when the shear rate is low as in coating. It is preferable because a coating film having an appearance can be formed. That is, it is preferable that the coating material has a viscosity that decreases as the shear rate increases.
  • the associative thickener generally has a hydrophilic part and a hydrophobic part in one molecule, and in an aqueous medium, the hydrophobic part is adsorbed on the surface of the pigment or emulsion particles in the paint, It is a thickener that effectively forms a thickening action by forming a network structure when hydrophobic portions are associated with each other.
  • the above-mentioned associative thickener usually forms a network structure by hydrophobic interaction and develops viscosity.
  • the hydrophobic interaction has a relatively weak binding force, when a large shear force is applied, the network structure is broken and the viscosity is lowered.
  • mold thickener has a viscosity characteristic that a viscosity falls with the increase in a shear rate.
  • the water-based paint generally contains a surfactant in order to disperse a hydrophobic resin component in water.
  • the viscosity due to the association type thickener becomes difficult to develop, and the formed coating film has high clarity and glitter. May be reduced, and was considered a problem. Specifically, since the viscosity when the water-based paint is applied to an object to be coated is low, a mixed layer is formed with the paint to be coated on the upper layer, and the clarity of the formed coating film is reduced. Or when the water-based paint contains a glitter pigment, the glitter pigment in the paint moves after the paint is applied, the orientation of the glitter pigment becomes irregular, and the flip-flop properties are reduced. In some cases, metallic unevenness may occur.
  • the viscosity at the time of application is increased by increasing the content of the associative thickener in the water-based paint, the viscosity when the shear rate is high is increased, and the paint is atomized. Since the coating particles at the time become large, the smoothness of the formed coating film may be inferior.
  • Patent Document 1 discloses a viscosity control agent comprising a hydrophobic part and a hydrophilic part obtained by hydrophobizing a hydrophilic polymer and / or obtained by hydrophobizing a hydrophobic polymer.
  • concentration dependency of the viscosity of the aqueous dispersion can be reduced, and further, the water-based paint using the viscosity control agent exhibits a stable flow property regardless of changes in the coating conditions, particularly temperature and humidity conditions. It is described that a coating film having a stable and excellent finish can be obtained. However, in some cases, the viscosity control agent has insufficient viscosity.
  • Patent Document 2 discloses associative thickening in which one molecule of alkenyl succinic anhydride or alkyl succinic anhydride is added per amino group to polyethylene glycol having at least two amino groups at the end of the molecule.
  • the viscosity of the agent and the water-based paint is not increased. It is described that it is excellent as an agent.
  • the associative thickener sometimes has insufficient viscosity.
  • Patent Document 3 describes that a urethane-based thickener having a specific structure is a thickener / viscosity modifier excellent in thickening and thixotropic properties.
  • the thixotropic property is the above-described viscosity characteristic in which the viscosity decreases as the shear rate increases.
  • the urethane-based thickener sometimes has insufficient viscosity.
  • a sufficient viscosity cannot be obtained, and the sharpness and flip-flop property of the formed coating film may be reduced, or metallic There was a tendency for unevenness to occur.
  • JP 2000-1662 A Japanese Patent Laid-Open No. 9-272796 JP 2002-69430 A
  • An object of the present invention is to provide a copolymer having a viscosity characteristic that exhibits high viscosity and has a viscosity characteristic that decreases as the shear rate increases, and in particular, in a water-based paint containing a surfactant, And a copolymer having a viscosity characteristic in which the viscosity decreases as the shear rate increases.
  • Another object of the present invention is to provide a coating material containing the above copolymer and capable of forming a coating film having excellent smoothness and sharpness.
  • Another object of the present invention is to provide a coating material that can form a coating film having excellent glossiness that contains the copolymer and the brightness pigment, has high flip-flop properties, and suppresses metallic unevenness. Moreover, it is providing the coating-film formation method using the said coating material, and the articles
  • a polymerizable unsaturated monomer having a graft polymer structure having a main chain and a side chain, and the main chain having a hydrophilic group is obtained by polymerizing a monomer component containing, and obtained by polymerizing a monomer component containing a polymerizable unsaturated monomer in which the side chain has a urea bond, a urethane bond, and / or an imide bond.
  • a copolymer containing a high molecular weight polymer has a viscosity characteristic that the viscosity is high and the viscosity decreases as the shear rate increases.
  • the copolymer has a viscosity characteristic that develops a viscosity even in a water-based paint containing a surfactant, and the viscosity decreases as the shear rate increases.
  • the present invention includes the following copolymer and a viscosity modifier comprising the copolymer, an aqueous paint containing the copolymer, a method for forming a coating film using the aqueous paint, and the aqueous paint. Articles are provided.
  • (M-1) (a) From the group consisting of a polymerizable unsaturated monomer (a1) having a urea bond, a polymerizable unsaturated monomer (a2) having a urethane bond, and a polymerizable unsaturated monomer (a3) having an imide bond Polymerize monomer component (I) comprising 5 to 100% by mass of at least one polymerizable unsaturated monomer selected and (b) 0 to 95% by mass of polymerizable unsaturated monomer other than the polymerizable unsaturated monomer (a).
  • a macromonomer having a basic skeleton made of a polymer having a number average molecular weight within the range of 1,000 to 10,000, and having a polymerizable unsaturated group, and (m-2) a hydrophilic group A copolymer obtained by copolymerizing a monomer component (m) containing a polymerizable unsaturated monomer having
  • Polymerizable unsaturated monomer (m-2) having a hydrophilic group is N-substituted (meth) acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, N-vinyl-2-pyrrolidone, 2-hydroxyethyl acrylate, Item 4.
  • the monomer component (m) is based on the total mass of the monomer component (m), the macromonomer (m-1) is 1 to 40% by mass, the polymerizable unsaturated monomer (m-2) having a hydrophilic group is 5 to 99 Item 1 or 2 above, wherein the polymerizable unsaturated monomer (m-3) other than the polymerizable unsaturated monomer (m-1) and (m-2) is 0 to 94% by mass.
  • An aqueous coating composition containing the copolymer according to any one of items 1 to 4 and a film-forming resin (A).
  • Item 6 The aqueous coating composition according to Item 5, wherein the film-forming resin (A) is a resin having an ester bond.
  • Item 7 The aqueous coating composition according to Item 5 or 6, wherein the film-forming resin (A) is a water-dispersible acrylic resin obtained by emulsion polymerization using a surfactant.
  • the film-forming resin (A) is a water-dispersible acrylic resin obtained by emulsion polymerization using a surfactant.
  • a method for forming a multilayer coating film comprising a step of heating a coating film to simultaneously cure both coating films.
  • a step of forming a first colored coating film by applying a first colored coating composition to an object to be coated (2) A step of forming the second colored coating film by applying the aqueous coating composition according to any one of the above items 5 to 7 on the uncured first colored coating film, (3) a step of applying a clear coat coating composition on the uncured second colored coating to form a clear coat coating; and (4) the uncured first colored coating,
  • a multilayer coating film forming method comprising a step of simultaneously heating and curing a cured second colored coating film and an uncured clear coat film.
  • Item having a multilayer coating film formed by the multilayer coating film forming method according to Item 9 or 10.
  • a viscosity modifier comprising the copolymer according to any one of items 1 to 4.
  • a polymerizable unsaturated monomer (a1) having a urea bond a polymerizable unsaturated monomer (a2) having a urethane bond
  • a polymerizable unsaturated monomer (a3) having an imide bond By polymerizing the monomer component (I) consisting of 5 to 100% by mass of the polymerizable unsaturated monomer of (b) and 0 to 95% by mass of the polymerizable unsaturated monomer other than the polymerizable unsaturated monomer (a), 1 A step of obtaining a macromonomer (m-1) having a basic skeleton composed of a polymer having a number average molecular weight within the range of 1,000
  • the copolymer of the present invention has high viscosity expression and has a viscosity characteristic that the viscosity decreases as the shear rate increases.
  • a viscosity characteristic that expresses viscosity and decreases with increasing shear rate.
  • the coating film which has the outstanding smoothness and sharpness can be formed.
  • the water-based paint of the present invention it is possible to form a coating film having excellent glitter with high flip-flop properties and suppressed metallic unevenness.
  • the present invention relates to (m-1) (a) a polymerizable unsaturated monomer (a1) having a urea bond, a polymerizable unsaturated monomer (a2) having a urethane bond, and a polymerizable having an imide bond.
  • polymerizable unsaturated monomer selected from the group consisting of unsaturated monomers (a3) and (b) 0 to 95% of polymerizable unsaturated monomers other than the polymerizable unsaturated monomer (a) % Having a basic skeleton composed of a polymer having a number average molecular weight within the range of 1,000 to 10,000 obtained by polymerizing the monomer component (I) comprising 1%, and having a polymerizable unsaturated group
  • a copolymer obtained by copolymerizing a monomer component (m) containing a monomer and (m-2) a polymerizable unsaturated monomer having a hydrophilic group.
  • the copolymer of the present invention has high viscosity expression and has a viscosity characteristic that the viscosity decreases as the shear rate increases.
  • a viscosity characteristic that expresses viscosity and decreases with increasing shear rate.
  • the copolymer of the present invention is preferably used as a viscosity modifier.
  • it can form the coating film which has the outstanding smoothness, clearness, and luster, it can be used conveniently as a viscosity regulator for coating materials.
  • the polymerizable unsaturated monomer means a monomer having one or more (for example, 1 to 4) polymerizable unsaturated groups.
  • the polymerizable unsaturated group means an unsaturated group capable of radical polymerization. Examples of the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl ether group, and an allyl group.
  • Polymerizable unsaturated monomer having a urea bond (a1)
  • the polymerizable unsaturated monomer (a1) having a urea bond is a polymerizable unsaturated monomer having a urea bond (also referred to as a urea bond) represented by —NH—CO—NH—.
  • the polymerizable unsaturated monomer (a1) having a urea bond can be obtained, for example, by reacting the following isocyanate unsaturated group-containing polymerizable unsaturated monomer with an amine compound.
  • Isocyanato group-containing polymerizable unsaturated monomer examples include 2- (meth) acryloyloxyethyl isocyanate; m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate; hydroxyl group-containing polymerizable unsaturated monomer. Reaction products of monomers and diisocyanate compounds; hydroxyl group-containing polymerizable unsaturated monomers, reaction products of diol compounds and diisocyanate compounds, and the like, which can be used alone or in combination of two or more.
  • the isocyanate unsaturated group-containing polymerizable unsaturated monomer is preferably 2-acryloyloxyethyl isocyanate and / or 2-methacryloyloxyethyl isocyanate, and more preferably 2-methacryloyloxyethyl isocyanate.
  • Examples of the hydroxyl group-containing polymerizable unsaturated monomer used in the reaction product of the hydroxyl group-containing polymerizable unsaturated monomer and the diisocyanate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 A monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms such as hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; the (meth) acrylic acid and 2 to 8 carbon atoms ⁇ -caprolactone modified product of monoesterified with dihydric alcohol of 8; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and the like. These can be used alone or in combination of two or more It is possible to use.
  • (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”.
  • diisocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Aliphatic diisocyanate compounds such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3 5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl
  • Aromatic, diisocyanate compounds such as benzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; m-phenylene diisocyanate, p -Phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4-TDI) or 2,6-tolylene diisocyanate (common name: 2, 6-TDI) or a mixture thereof, an aromatic diisocyanate compounds; methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene Aromatic,
  • the reaction of the hydroxyl group-containing polymerizable unsaturated monomer and the diisocyanate compound can be performed by a known method.
  • diol compound used in the reaction product of the hydroxyl group-containing polymerizable unsaturated monomer, diol compound, and diisocyanate compound examples include alkyl diol, polyether diol, polyester diol, polycarbonate diol, and the like. It can be used alone or in combination of two or more.
  • the reaction product may react these components at a blending ratio in which the amount of the isocyanate group derived from the diisocyanate compound is larger than the total amount of the hydroxyl group derived from the hydroxyl group-containing polymerizable unsaturated monomer and the diol compound. Can be obtained.
  • the reaction product is usually a compound having two or more urethane bonds and isocyanato groups in one molecule.
  • examples of commercially available isocyanato group-containing polymerizable unsaturated monomers include “Karenz MOI”, “Karenz AOI”, “Karenz MOI-EG” (above, Showa Denko).
  • the amine compound is preferably a primary amine compound or a secondary amine compound, and more preferably a primary amine compound.
  • the amine compound may have a hydroxyl group.
  • Examples of the primary amine compound include ethylamine, propylamine (n-propylamine, isopropylamine), butylamine (n-butylamine, sec-butylamine, tert-butylamine), n-pentylamine, 1-methylbutylamine, 1 -Ethylpropylamine, 2-ethylbutylamine, hexylamine, n-octylamine, 2-ethylhexylamine, decylamine, stearylamine, cyclohexylamine, ethanolamine, 6-aminohexanol, p-methoxybenzylamine, methoxypropylamine, 3 , 4-dimethoxyphenylethylamine, 2,5-dimethoxyaniline, furfurylamine, tetrahydrofurfurylamine, benzylamine, aniline, hexamethylenediamine, etc.
  • Examples of the secondary amine compound include diethylamine, dipropylamine, dibutylamine (di-n-butylamine, di-sec-butylamine, di-tert-butylamine), diisopropylamine, diisobutylamine, dipentylamine, dioctyl.
  • Amine didecylamine, distearylamine, N-ethyl-1,2-dimethylpropylamine, N-methylbutylamine, N-butylethylamine, diethanolamine, diisopropanolamine , 2- (methylamino) ethanol, 2- (isopropylamino) ethanol, 2- (ethylamino) ethanol, piperidine, hexamethyleneimine, morpholine and the like. In combination can be used.
  • the reaction between the isocyanato group-containing polymerizable unsaturated monomer and the amine compound is carried out by the equivalent ratio of the isocyanato group present in the isocyanato group-containing polymerizable unsaturated monomer and the active hydrogen present in the amine compound (active hydrogen / Isocyanato group) at a ratio of 0.5 / 1 to 2/1, preferably 0.7 / 1 to 1.5 / 1, more preferably 0.8 / 1 to 1.2 / 1. And can be carried out by a known method.
  • the reaction of the above-mentioned isocyanato group-containing polymerizable unsaturated monomer and the amine compound can be carried out by a known method by mixing both, raising the temperature as desired. This reaction is desirably carried out at a temperature of 5 to 70 ° C., preferably 20 to 50 ° C.
  • the above reaction components can be mixed by a known method, for example, by adding an amine compound to an isocyanate group-containing polymerizable unsaturated monomer. Moreover, the addition of the above reaction components can be carried out in several stages as desired.
  • the above reaction can be performed in the presence of an organic solvent such as acetone, methyl isobutyl ketone, benzene, toluene, xylene, tetrahydrofuran, an aliphatic hydrocarbon solvent (petroleum ether, etc.) and the like.
  • an organic solvent such as acetone, methyl isobutyl ketone, benzene, toluene, xylene, tetrahydrofuran, an aliphatic hydrocarbon solvent (petroleum ether, etc.) and the like.
  • polymerizable unsaturated monomer (a1) having a urea bond examples include, for example, 2- (3-ethylureido) ethyl methacrylate obtained by reacting 2-methacryloyloxyethyl isocyanate and ethylamine; 2-methacryloyloxy 2- (3-isopropylureido) ethyl methacrylate obtained by reacting ethyl isocyanate and isopropylamine; 2- (3-butylureido) ethyl methacrylate obtained by reacting 2-methacryloyloxyethyl isocyanate and butylamine; 2-methacryloyl 2- [3- (2-ethylhexyl) ureido] ethyl methacrylate obtained by reacting oxyethyl isocyanate and 2-ethylhexylamine; 2-methacryloyloxyethyl isocyanate 2- (3-e
  • Polymerizable unsaturated monomer having urethane bond (a2)
  • the polymerizable unsaturated monomer (a2) having a urethane bond is a polymerizable unsaturated monomer having a urethane bond represented by —NH—CO—O—.
  • the polymerizable unsaturated monomer (a2) having a urethane bond is, for example, a method of reacting an isocyanate group-containing polymerizable unsaturated monomer and a hydroxyl group-containing compound; reacting a hydroxyl group-containing polymerizable unsaturated monomer and an isocyanate group-containing compound. It can obtain by the method of making it.
  • the isocyanate unsaturated group-containing polymerizable unsaturated monomer that can be used in the method of reacting the isocyanate unsaturated group-containing polymerizable unsaturated monomer with the hydroxyl group-containing compound is described in the explanation column of the polymerizable unsaturated monomer having a urea bond (a1).
  • Examples include the isocyanate group-containing polymerizable unsaturated monomers described.
  • the isocyanato group-containing polymerizable unsaturated monomer is 2-methacryloyloxyethyl isocyanate.
  • hydroxyl group-containing compound examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, Alkanols such as decanol, heptadecanol, octadecanol; propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polypropylene glycol monomethyl ether, polyoxyethylene Ethers such as polyoxypropylene monomethyl ether Containing monools: ethylene glycol, propylene glycol, polyethylene glycol, but
  • the hydroxyl group-containing compound is preferably an alkanol having 2 to 8 carbon atoms.
  • the alkanol having 2 to 8 carbon atoms include ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, n-octanol, 2-ethyl-1-hexanol, etc.
  • ethanol, butanol, 2 -Ethyl-1-hexanol is preferred.
  • Examples of the hydroxyl group-containing polymerizable unsaturated monomer used in the method of reacting the hydroxyl group-containing polymerizable unsaturated monomer and the isocyanato group-containing compound include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Monoesterified products of (meth) acrylic acid such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and dihydric alcohols having 2 to 8 carbon atoms; the (meth) acrylic acid ⁇ -caprolactone modified product of monoesterified product of dihydric alcohol having 2 to 8 carbon atoms; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end
  • These may be used alone or in combination of two or more It can be used in conjunction look. Among these, from the viewpoint of stability during
  • the isocyanate group-containing compound includes, for example, the diisocyanate compound described in the description of the polymerizable unsaturated monomer (a1) having a urea bond; the diisocyanate compound, and an active hydrogen-containing compound such as a monoalcohol or an amine.
  • the monoisocyanate compound etc. which are obtained by making these react are mentioned, These can be used individually or in combination of 2 or more types.
  • Polymerizable unsaturated monomer having an imide bond examples include hexahydrophthalimide ethyl acrylate (Aronix M-140: product of Toa Gosei Co., Ltd.), hexahydrophthalimide propylene acrylate, phthalimide ethyl methacrylate, and the like. Or it can use in combination of 2 or more types. Moreover, this monomer can also be synthesize
  • the polymerizable unsaturated monomer (b) is other than the polymerizable unsaturated monomer (a1) having a urea bond, the polymerizable unsaturated monomer (a2) having a urethane bond, and the polymerizable unsaturated monomer (a3) having an imide bond.
  • Examples of the polymerizable unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) Acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate,
  • the monomer component (I) is composed of the polymerizable unsaturated monomer (a1) having a urea bond, the polymerizable unsaturated monomer (a2) having a urethane bond, and the polymerizable unsaturated monomer (a3) having an imide bond. It comprises 5 to 100% by mass of at least one polymerizable unsaturated monomer (a) selected, and 0 to 95% by mass of a polymerizable unsaturated monomer (b) other than the polymerizable unsaturated monomer (a).
  • the blending ratio of the polymerizable unsaturated monomers (a) and (b) is such that the viscosity of the obtained copolymer and the coating film formed by the paint containing the copolymer are as follows. From the viewpoint of improvement in smoothness, sharpness, flip-flop properties and water resistance, and suppression of metallic unevenness, the following ranges are preferable based on the total mass of the monomer component (I).
  • At least one polymerizability selected from the group consisting of a polymerizable unsaturated monomer (a1) having a urea bond, a polymerizable unsaturated monomer (a2) having a urethane bond, and a polymerizable unsaturated monomer (a3) having an imide bond
  • a polymerizable unsaturated monomer (a1) having a urea bond a polymerizable unsaturated monomer (a2) having a urethane bond
  • the monomer component (I) preferably contains a hydroxyl group-containing polymerizable unsaturated monomer as at least a part thereof from the viewpoint of the sharpness and water resistance of the formed coating film.
  • the polymerizable unsaturated monomer (b) contains a hydroxyl group-containing polymerizable unsaturated monomer as at least a part thereof.
  • the hydroxyl group-containing polymerizable unsaturated monomer As the hydroxyl group-containing polymerizable unsaturated monomer, the hydroxyl group-containing polymerizable unsaturated monomer exemplified in the explanation of the polymerizable unsaturated monomer (b) can be used. ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred, and 2-hydroxyethyl methacrylate is more preferred.
  • the use ratio of the hydroxyl group-containing polymerizable unsaturated monomer is determined from the monomer component ( It is suitable that the content is in the range of 5 to 60% by mass, preferably 10 to 45% by mass, more preferably 15 to 30% by mass, based on the total mass of I).
  • the hydroxyl value of the polymer obtained by polymerizing the monomer component (I) depends on the sharpness and water resistance of the coating film to be formed. From the viewpoint of properties, it is preferable to be within the range of 20 to 260 mgKOH / g, preferably 40 to 200 mgKOH / g, more preferably 60 to 130 mgKOH / g.
  • the monomer component (I) contains a polymerizable unsaturated monomer having an alkyl group having 4 to 24 carbon atoms as at least a part thereof from the viewpoint of the sharpness and water resistance of the formed coating film. It is preferable. Specifically, it is preferable that the polymerizable unsaturated monomer (b) contains a polymerizable unsaturated monomer having an alkyl group having 4 to 24 carbon atoms as at least a part thereof.
  • polymerizable unsaturated monomer having an alkyl group having 4 to 24 carbon atoms for example, a monoesterified product of (meth) acrylic acid and a monohydric alcohol having an alkyl group having 4 to 24 carbon atoms can be used.
  • Examples of the polymerizable unsaturated monomer having an alkyl group having 4 to 24 carbon atoms include n-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate from the viewpoint of smoothness and sharpness of the resulting coating film. Is preferred.
  • the use ratio of the polymerizable unsaturated monomer having an alkyl group having 4 to 24 carbon atoms is formed. From the viewpoint of smoothness and sharpness of the coating film, it is in the range of 1 to 95% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the total weight of the monomer component (I). It is preferable that
  • the macromonomer (m-1) is a macromonomer having a polymer and a polymerizable unsaturated group, and is obtained by polymerizing the monomer component (I) to 1,000 to 10,0. It is a macromonomer that is a polymer having a number average molecular weight in the range of 000.
  • the macromonomer is a high molecular weight monomer having a polymerizable unsaturated group, and preferably a high molecular weight monomer having a polymerizable unsaturated group at the end of the polymer. Therefore, the macromonomer (m-1) has a basic skeleton composed of the above polymer and has a structure having at least one, preferably one polymerizable unsaturated group, preferably at the terminal of the polymer.
  • the polymerizable unsaturated group contained in the macromonomer (m-1) means an unsaturated group capable of radical polymerization.
  • examples of the polymerizable unsaturated group include a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group.
  • the macromonomer (m-1) preferably has a number average molecular weight in the range of 1,000 to 10,100. Of these, the number average molecular weight is preferably in the range of 1,000 to 5,000, preferably 1,000 to 3,000, from the viewpoint of smoothness and sharpness of the resulting coating film.
  • the number average molecular weight of the macromonomer (m-1) is adjusted by, for example, the amount of chain transfer agent used, the amount of polymerization initiator used, the reaction temperature, the reaction time, etc. when the monomer component (I) is polymerized. be able to.
  • the macromonomer (m-1) can be obtained by a method known per se. Specifically, for example, it can be obtained by the following method (1), method (2), method (3) and the like.
  • Method (1) When polymerizing the monomer component (I), a polymer is obtained by performing polymerization in the presence of a chain transfer agent containing a first chemically reactive group such as a carboxyl group, a hydroxyl group, and an amino group. A first chemically reactive group is introduced at the end of the. Next, by reacting the obtained polymer with a polymerizable unsaturated monomer having a second chemically reactive group capable of reacting with the first chemically reactive group in the polymer, a macromonomer (m -1) can be obtained.
  • a chain transfer agent containing a first chemically reactive group such as a carboxyl group, a hydroxyl group, and an amino group.
  • a first chemically reactive group is introduced at the end of the.
  • a macromonomer (m -1) can be obtained.
  • chain transfer agent containing the first chemically reactive group such as a carboxyl group, a hydroxyl group, and an amino group
  • chain transfer agent containing the first chemically reactive group such as a carboxyl group, a hydroxyl group, and an amino group
  • examples of the chain transfer agent containing the first chemically reactive group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptoethanol, 2-aminoethane. Thiols and the like can be suitably used.
  • Examples of the polymerizable unsaturated monomer having a second chemically reactive group for reacting with the first chemically reactive group in the copolymer to introduce a polymerizable unsaturated group include the first chemical When the reactive group is a carboxy group, an epoxy group-containing polymerizable unsaturated monomer; when the first chemically reactive group is a hydroxyl group; an isocyanato group-containing polymerizable unsaturated monomer; When the functional group is an amino group, an epoxy group-containing polymerizable unsaturated monomer can be preferably used.
  • epoxy group-containing polymerizable unsaturated monomer for example, glycidyl acrylate, glycidyl methacrylate and the like can be suitably used.
  • isocyanato group-containing polymerizable unsaturated monomer for example, 2- (meth) acryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate and the like can be preferably used.
  • the macromonomer (m-1) can be obtained by catalytic chain transfer polymerization using a metal complex (Catalytic Chain Transfer Polymerization, CCTP method).
  • the CCTP method is described in, for example, Japanese Patent Publication No. 6-23209, Japanese Patent Publication No. 7-35411, Japanese Patent Publication No. 9-501457, Japanese Patent Application Laid-Open No. 9-176256, Macromolecules 1996, 29, 8083-8089.
  • the macromonomer (m-1) can be produced by catalytic chain transfer polymerization of the monomer component (I) in the presence of a metal complex.
  • the catalytic chain transfer polymerization can be performed by, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, or the like. Moreover, in the case of superposition
  • the metal complex examples include a cobalt complex, an iron complex, a nickel complex, a ruthenium complex, a rhodium complex, a palladium complex, a rhenium complex, and an iridium complex.
  • the cobalt complex is efficiently used as a catalytic chain transfer agent.
  • the amount of the metal complex used is not particularly limited, but is usually 1 ⁇ 10 ⁇ 6 to 1 part by mass, preferably 1 ⁇ 10 ⁇ 4 based on 100 parts by mass of the total mass of the monomer component (I). It is suitable to be within the range of 0.5 parts by mass.
  • radical polymerization initiator examples include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxide.
  • Organic peroxides such as oxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile Azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4- Cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis ⁇ 2-methyl-N- [2- (1-hydroxy Butyl)]-propionamide ⁇ and the like; and persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate.
  • persulfates such as potassium persulfate
  • the amount of the radical polymerization initiator is not particularly limited, but is usually 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the monomer component (I). It is suitable to be in the range of 8 parts by mass, more preferably 0.1-6 parts by mass.
  • the macromonomer (m-1) can be obtained by an addition cleavage type chain transfer polymerization method using an addition cleavage type chain transfer agent.
  • the addition-cleavage type chain transfer polymerization method is described in, for example, JP-A-7-2954.
  • the macromonomer (m-1) can be produced by subjecting the monomer component (I) to addition-cleavage chain transfer polymerization in the presence of the addition-cleavage chain transfer agent.
  • the addition-cleavage chain transfer polymerization can be performed by, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, or the like.
  • a radical polymerization initiator can be used together as needed.
  • addition-cleavage chain transfer agent for example, 2,4-diphenyl-4-methyl-1-pentene (sometimes abbreviated as “ ⁇ -methylstyrene dimer” or “MSD”) is preferably used. be able to.
  • the compounding amount of the addition-cleavage chain transfer agent is not particularly limited, but is usually 1 to 20 parts by mass, preferably 2 to 15 parts by mass, based on 100 parts by mass of the total mass of the monomer component (I). Parts, more preferably in the range of 3 to 10 parts by weight.
  • radical polymerization initiator for example, the radical polymerization initiator described in the explanation of the method (2) can be used. These polymerization initiators can be used alone or in combination of two or more.
  • the blending amount of the radical polymerization initiator is not particularly limited, but is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight based on 100 parts by weight of the total weight of the monomer component (I). More preferably, it is within the range of 3 to 10 parts by mass.
  • the polymerization temperature varies depending on the kind of the radical polymerization initiator, but is in the range of 60 to 200 ° C., preferably 80 to 180 ° C., more preferably 90 to 170 ° C. Is preferred.
  • the temperature may be different between the first half and the second half of the polymerization, and the polymerization may be performed while gradually changing the temperature.
  • the method (1) comprises a step of polymerizing the monomer component (I) to obtain a polymer, and a reaction between the obtained polymer and a polymerizable unsaturated monomer. Two reaction steps including a step of introducing a polymerizable unsaturated group into the polymer are necessary.
  • the method (2) uses a metal complex, catalytic chain transfer polymerization may occur during the production of a copolymer (graft polymer) described later, and the resulting copolymer may be colored. is there.
  • the macromonomer (m-1) is an addition-cleavage-type chain using the addition-cleavage-type chain transfer agent of the method (3). It is preferable to obtain by a transfer polymerization method.
  • macromonomer (m-1) can be used alone or in combination of two or more.
  • Polymerizable unsaturated monomer having a hydrophilic group (m-2) examples include N-substituted (meth) acrylamide, a polymerizable unsaturated monomer having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone. , 2-hydroxyethyl acrylate, carboxyl group-containing polymerizable unsaturated monomer, polymerizable unsaturated monomer having a sulfonic acid group, phosphoric acid group-containing polymerizable unsaturated monomer, and the like. Can be used in combination.
  • polymerizable unsaturated monomer (m-2) having a hydrophilic group N-substituted (meth) acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, N-vinyl-2-pyrrolidone, 2- At least one polymerizable unsaturated monomer selected from the group consisting of hydroxyethyl acrylate, acrylic acid and methacrylic acid can be suitably used. These can be used alone or in combination of two or more.
  • the content ratio of the macromonomer (m-1) and the polymerizable unsaturated monomer (m-2) having a hydrophilic group is determined depending on the smoothness, sharpness, brightness of the coating film to be formed. From the viewpoint of water resistance and water resistance, it is preferably within the following range based on the total mass of the monomer component (m): Macromonomer (m-1): 1 to 40% by mass, preferably 3 to 29% by mass, more preferably 5 to 15% by mass, Polymerizable unsaturated monomer having a hydrophilic group (m-2): 5 to 99% by mass, preferably 10 to 97% by mass, more preferably 20 to 95% by mass.
  • N-substituted (meth) acrylamide examples include N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide butyl ether, N-methylolmethacrylamide butyl ether, N-ethylacrylamide, N-ethylmethacrylamide, N- n-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-hydroxymethyl Acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N, N Dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-methyl, N-ethylacrylamide
  • Nn-propyl acrylamide, Nn-propyl methacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-hydroxyethyl acrylamide from the viewpoint of smoothness and sharpness of the formed coating film N-hydroxyethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide are preferred, N, N-dimethylacrylamide, N, N More preferred is dimethylmethacrylamide.
  • the polymerizable unsaturated monomer having a polyoxyalkylene chain is a monomer containing a polyoxyalkylene chain and a polymerizable unsaturated group in one molecule.
  • polyoxyalkylene chain examples include a polyoxyethylene chain, a polyoxypropylene chain, a chain composed of a polyoxyethylene block and a polyoxypropylene block, and a chain formed by randomly bonding polyoxyethylene and polyoxypropylene.
  • These polyoxyalkylene chains generally have a molecular weight in the range of about 100 to 5,000, preferably about 200 to 4,000, more preferably about 300 to 3,000. It is.
  • Representative examples of the polymerizable unsaturated monomer having a polyoxyalkylene chain include, for example, the following general formula (1) [Wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.
  • R 3 represents an alkylene group having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, more preferably 2 carbon atoms, and m is 3 to 150, preferably 5 to 80, more preferably 8 to 50 carbon atoms. Represents an integer, and m oxyalkylene units (O—R 3 ) may be the same as or different from each other]
  • the polymerizable unsaturated monomer shown by these can be mentioned.
  • polymerizable unsaturated monomer represented by the general formula (1) include, for example, tetraethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, n- Butoxytriethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytetrapyroprene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene ( (Lopylene) glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glyco
  • polyethylene glycol (meth) acrylate, polyethylene (propylene) glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene (propylene) glycol from the viewpoint of smoothness and sharpness of the formed coating film (Meth) acrylate is preferable, and polyethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate are more preferable.
  • the polymerizable unsaturated monomer having a polyoxyalkylene chain generally has a molecular weight in the range of about 300 to 6,000, preferably about 400 to 5,000, more preferably about 450 to 3,500. Is preferred.
  • carboxyl group-containing polymerizable unsaturated monomer examples include (meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate and the like, and these are used alone or in combination of two or more. be able to.
  • Examples of the polymerizable unsaturated monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; A sodium salt, an ammonium salt, etc. are mentioned, These can be used individually or in combination of 2 types or more, respectively.
  • Examples of the phosphoric acid group-containing polymerizable unsaturated monomer include 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, and the like. These can be used alone or in combination of two or more.
  • the other polymerizable unsaturated monomer (m-3) is a polymerizable unsaturated monomer other than the macromonomer (m-1) and the polymerizable unsaturated monomer (m-2) having a hydrophilic group.
  • the other polymerizable unsaturated monomer (m-3) can be appropriately selected and used as required according to the properties desired for the copolymer.
  • alkyl or cycloalkyl (meth) acrylate for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (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 (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth)
  • (Vi) Polymerizable unsaturated monomer having an alkoxysilyl group For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - ( (Meth) acryloyloxypropyltriethoxysilane and the like.
  • (Vii) Polymerizable unsaturated monomer having a fluorinated alkyl group: For example, perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
  • (Viii) A polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group.
  • (Ix) Vinyl compound: For example, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.
  • (X) Hydroxyl-containing polymerizable unsaturated monomer (Meth) such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Monoesterified product of acrylic acid and dihydric alcohol having 2 to 8 carbon atoms; ⁇ -caprolactone modified product of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms; allyl alcohol and the like.
  • Nitrogen-containing polymerizable unsaturated monomer For example, (meth) acrylonitrile, (meth) acrylamide, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, glycidyl (meth) ) Adducts of acrylate and amine compounds.
  • Epoxy group-containing polymerizable unsaturated monomer for example, 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.
  • (Xiv) Polymerizable unsaturated monomer having a UV-absorbing functional group: For example, 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′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
  • (Xv) Light-stable polymerizable unsaturated monomer For example, 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-tetramethylpiperidine and the
  • polymerizable unsaturated monomer having a carbonyl group for example, acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like.
  • Polymerizable unsaturated monomer having an acid anhydride group For example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
  • the polymerizable unsaturated monomer (m-3) preferably contains the hydroxyl group-containing polymerizable unsaturated monomer (x) as at least a part thereof.
  • the hydroxyl group-containing polymerizable unsaturated monomer (x) is preferably 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate. -Hydroxyethyl methacrylate is more preferred.
  • the content of the hydroxyl group-containing polymerizable unsaturated monomer (x) is the amount of the monomer component (m). It is suitable to be within the range of 5 to 79% by mass, preferably 10 to 57% by mass, more preferably 15 to 40% by mass, based on the total mass.
  • Monomer component (m) In the monomer component (m), the content ratios of the macromonomer (m-1), the polymerizable unsaturated monomer (m-2) having a hydrophilic group, and other polymerizable unsaturated monomers (m-3) are obtained.
  • Monomer component (m) from the viewpoint of increasing the viscosity of the copolymer and improving the smoothness, sharpness, flip-flop properties and water resistance of the coating film formed by the coating material containing the copolymer, and suppressing metallic unevenness Based on the total mass of Macromonomer (m-1): 1 to 40% by mass, preferably 3 to 29% by mass, more preferably 5 to 15% by mass, Polymerizable unsaturated monomer having a hydrophilic group (m-2): 5 to 99% by mass, preferably 10 to 97% by mass, more preferably 20 to 95% by mass, Polymerizable unsaturated monomer (m-3) other than macromonomer (m-1) and polymerizable unsaturated monomer (m-2) having a hydrophilic group: 0 to 94% by mass, preferably 0 to 87% by mass, Preferably 0 to 75% by mass.
  • the copolymer of the present invention is usually a graft polymer having a main chain and a side chain, and the polymer in the macromonomer (m-1) forms a side chain portion and has a polymerizability having the hydrophilic group.
  • the unsaturated monomer (m-2) and the other polymerizable unsaturated monomer (m-3) form the main chain portion.
  • the copolymer of the present invention comprises the macromonomer (m-1), a polymerizable unsaturated monomer (m-2) having a hydrophilic group, and other polymerizable compounds blended as necessary.
  • a monomer component (m) comprising an unsaturated monomer (m-3) by a method known per se, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, or the like. can do.
  • a solution polymerization method that can be carried out by a relatively easy operation is preferable.
  • Examples of the polymerization initiator used when copolymerizing the monomer component (m) include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, Di-tert-amyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide, etc.
  • the amount of the polymerization initiator used is usually 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total mass of the monomer components (m).
  • the method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be included in the monomer mixture or the reaction solvent in advance, or may be added all at once during the polymerization, or may be added dropwise.
  • an organic solvent which is less likely to cause chain transfer to the solvent and is water-soluble is preferable.
  • organic solvents include ester solvents such as ethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; ketone solvents such as acetone and methyl ethyl ketone; methanol, ethanol, isopropanol, n-butanol, sec-butanol, and isobutanol.
  • Alcohol solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, etc .; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether
  • glycol ether solvents such as Is, it can be used either alone or in combination of two or more. Of these, ether solvents and glycol ether solvents are preferred.
  • the amount of the organic solvent used in the polymerization reaction is usually 500 parts by weight or less, preferably 50 to 400 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the total mass of the monomer components (m). It is preferable to be within the range of parts.
  • the weight average molecular weight of the copolymer of the present invention is 20 from the viewpoints of thickening of the copolymer obtained and smoothness, sharpness and glitter of the coating film formed by the coating material containing the copolymer. It is suitable that it is within the range of 1,000 to 1,000,000, preferably 50,000 to 600,000, more preferably 100,000 to 400,000.
  • the number average molecular weight of the polymer and macromonomer (m-1) obtained by copolymerization of the monomer component (I) and the weight average molecular weight of the copolymer of the present invention are expressed by gel permeation chromatography. It is the value obtained by converting the retention time (retention capacity) measured using the graph (GPC) into the molecular weight of polystyrene by the retention time (retention capacity) of standard polystyrene having a known molecular weight measured under the same conditions.
  • the number average molecular weight of the polymer and macromonomer (m-1) obtained by copolymerization of the monomer component (I) is “HLC-8120GPC” (trade name, Tosoh Corporation) as a gel permeation chromatograph. 4 columns, “TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel G2000HXL” (trade names, all manufactured by Tosoh Corporation) are used as detectors. Using a differential refractometer, it can be measured under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 mL / min.
  • the weight average molecular weight of the copolymer of the present invention was determined by using “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph, and “TSKgel GMHHR-L” (product) as a column. Name, manufactured by Tosoh Corporation), using a differential refractometer as a detector, mobile phase: dimethylformamide (containing 10 mM each of lithium bromide and phosphoric acid), measurement temperature: 25 ° C., flow rate: It can be measured under the condition of 1 mL / min.
  • the aqueous coating composition of the present invention has a viscosity characteristic that the viscosity is high and the viscosity decreases with an increase in the shear rate. Therefore, the copolymer of the present invention is suitably used as a viscosity modifier for an aqueous coating. be able to.
  • a water-based paint containing a surfactant also has a viscosity characteristic in which the viscosity develops and the viscosity decreases with increasing shear rate.
  • the aqueous coating material containing the copolymer of the present invention can form a coating film having excellent smoothness and sharpness.
  • the aqueous coating composition according to the present invention (hereinafter sometimes abbreviated as “present coating”) usually contains the copolymer and a film-forming resin (A).
  • Film-forming resin (A) As the film-forming resin (A), a water-soluble or water-dispersible film-forming resin known per se that has been conventionally used as a binder component of water-based paints can be used.
  • the film-forming resin (A) include acrylic resin, polyester resin, alkyd resin, silicon resin, fluororesin, epoxy resin, and polyurethane resin.
  • a film-forming resin (A) having high smoothness, sharpness, flip-flop properties, excellent appearance with suppressed metallic unevenness, and excellent water resistance can be formed.
  • a water-dispersible film-forming resin is generally obtained by dispersing a relatively hydrophobic film-forming resin in an aqueous medium, and therefore, compared with a water-soluble film-forming resin imparted with high hydrophilicity.
  • a coating film excellent in water resistance is formed.
  • the copolymer of the present invention since the copolymer of the present invention has a relatively high molecular weight side chain, it forms a network structure with the relatively hydrophobic film-forming resin as described above, and develops a viscosity, so that it has smoothness, freshness, It is possible to form a coating film having excellent visual appearance and high flip-flop properties and excellent metallic unevenness.
  • the water-dispersible film-forming resin is preferably a film-forming resin to which water-dispersibility is imparted by a surfactant from the viewpoint of the storage stability of the resulting paint.
  • the copolymer of the present invention has a viscosity characteristic that develops viscosity even in a water-based paint containing a surfactant and decreases with increasing shear rate.
  • a water-based coating composition containing a film-forming resin imparted with water dispersibility by an agent is excellent in storage stability, smoothness, sharpness and flip-flop properties, and excellent in metallic unevenness. It is possible to form a coating film having an excellent appearance and excellent water resistance.
  • the film-forming resin imparted with water dispersibility by the surfactant for example, an acrylic resin produced by an emulsion polymerization method using a surfactant can be suitably used.
  • the film-forming resin (A) is preferably a resin having an ester bond from the viewpoint of the smoothness, sharpness, flip-flop property and metallic unevenness of the coating film to be formed.
  • the resin having an ester bond for example, a copolymer obtained by polymerizing a monomer mixture containing a polymerizable unsaturated monomer having an ester bond, an acrylic resin, a polyester resin, and the like can be preferably used. However, acrylic resin is preferred.
  • the aqueous coating composition containing the copolymer of the present invention and a film-forming resin having an ester bond has high smoothness, sharpness and flip-flop properties, and has an excellent appearance with suppressed metallic unevenness.
  • a coating film can be formed is the affinity between the ester bond in the polymerizable unsaturated monomer (a) present in the side chain of the copolymer of the present invention and the ester bond in the film-forming resin (A). It is presumed that a high viscosity is developed because a network structure is formed that is high and is bonded more firmly.
  • the film-forming resin (A) preferably has a crosslinkable functional group such as a hydroxyl group, a carboxyl group, or an epoxy group.
  • the aqueous coating composition of the present invention preferably further contains a curing agent (B) described later.
  • the film-forming resin (A) usually has a crosslinkable functional group such as a hydroxyl group, a carboxyl group, an epoxy group, and the curing.
  • a resin (base resin) that can form a cured film by reacting with the agent (B) is used.
  • the base resin examples include acrylic resin, polyester resin, alkyd resin, and polyurethane resin.
  • the base resin is preferably a hydroxyl group-containing resin, and more preferably a hydroxyl group-containing acrylic resin (A1) and / or a hydroxyl group-containing polyester resin (A2).
  • the ratio of the combined use is about 20 to 80% by mass, particularly about 30 to 70% by mass based on the total amount of the hydroxyl group-containing acrylic resin (A1) and the hydroxyl group-containing polyester resin (A2).
  • the latter is preferably about 80 to 20% by mass, particularly about 70 to 30% by mass.
  • the acid value is preferably about 5 to 150 mgKOH / g, more preferably about 10 to 100 mgKOH / g, More preferably, it is about ⁇ 80 mg KOH / g.
  • the hydroxyl value is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 180 mgKOH / g, and about 5 to 170 mgKOH / g. Is more preferable.
  • hydroxyl group-containing acrylic resin (A1) for example, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer can be obtained by a method known per se, for example, It can be produced by copolymerization by a method such as a solution polymerization method in an organic solvent, an emulsion polymerization method in water, or a miniemulsion polymerization method in water. Among these, when used as a film-forming resin for water-based paints, an emulsion polymerization method in water is preferable because the number of steps required for producing the resin is small.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule.
  • Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • the hydroxyl group-containing polymerizable unsaturated monomer has a hydroxyl group-containing polymerization having an ester bond. It is preferably a polymerizable unsaturated monomer.
  • the hydroxyl group-containing polymerizable unsaturated monomer having an ester bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • a monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms a monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms; a ⁇ -caprolactone modified product of a monoesterified product of the (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms
  • polyoxyalkylene glycol modified products of monoesters of the (meth) acrylic acid and dihydric alcohols having 2 to 8 carbon atoms having 2 to 8 carbon atoms.
  • monoesterified products of (meth) acrylic acid and dihydric alcohols having 2 to 8 carbon atoms are preferred, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) ) Acrylate and 4-hydroxybutyl (meth) acrylate are more preferred.
  • Examples of the other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer are exemplified as the component (m-2) and the component (m-3) in the description of the copolymer.
  • the polymerizable unsaturated monomers monomers (i) to (ix) and (xi) to (xvii) that are polymerizable unsaturated monomers other than the hydroxyl group-containing polymerizable unsaturated monomer can be used. These polymerizable unsaturated monomers can be used alone or in combination of two or more.
  • the hydroxyl group-containing acrylic resin (A1) preferably has an amide group.
  • the hydroxyl group-containing acrylic resin having an amide group includes, for example, (meth) acrylamide, N, N-dimethylamino as one of other polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer. It can be produced by using an amide group-containing polymerizable unsaturated monomer such as propyl (meth) acrylamide, methylene bis (meth) acrylamide, or ethylene bis (meth) acrylamide.
  • the proportion of the hydroxyl group-containing polymerizable unsaturated monomer used in the production of the hydroxyl group-containing acrylic resin (A1) is preferably about 1 to 50% by mass, preferably about 2 to 40% by mass, based on the total amount of monomer components. Is more preferable, and about 3 to 30% by mass is more preferable.
  • the hydroxyl group-containing acrylic resin (A1) preferably has an acid value of about 0.1 to 200 mgKOH / g from the viewpoint of storage stability of the paint, water resistance of the resulting coating film, and the like. g is more preferable, and about 5 to 100 mgKOH / g is more preferable.
  • the hydroxyl group-containing acrylic resin (A1) preferably has a hydroxyl value of about 0.1 to 200 mgKOH / g, from the viewpoint of water resistance of the resulting coating film, and about 2 to 150 mgKOH / g. More preferred is about 5 to 100 mg KOH / g.
  • the hydroxyl group-containing acrylic resin (A1) includes (b-1) 5 to 70% by mass of a hydrophobic polymerizable unsaturated monomer, and (b-2) 0.1 to 25% by mass of a hydroxyl group-containing polymerizable unsaturated monomer.
  • (B-3) 0.1-20% by mass of a carboxyl group-containing polymerizable unsaturated monomer and (b-4) polymerizable unsaturated monomers other than the above polymerizable unsaturated monomers (b-1) to (b-3)
  • Water-dispersible hydroxyl group-containing acrylic resin (A1 ′) having an acid value of 1 to 100 mgKOH / g and a hydroxyl value of 1 to 100 mgKOH / g, obtained by copolymerizing the monomer component (b) comprising 0 to 94.8% by mass of the monomer Can be preferably used.
  • hydrophobic polymerizable unsaturated monomer (b-1) is a polymerizable unsaturated group having a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 or more carbon atoms, preferably 6 to 18 carbon atoms. Monomers having a hydrophilic group such as a hydroxyl group-containing polymerizable unsaturated monomer are excluded.
  • Examples of the monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl.
  • the hydrophobic polymerizable unsaturated monomer (b-1) is n-butyl (meth) acrylate
  • 2 -It is preferably at least one polymerizable unsaturated monomer selected from the group consisting of ethylhexyl (meth) acrylate and styrene.
  • Hydroxyl-containing polymerizable unsaturated monomer (b-2) The hydroxyl group-containing polymerizable unsaturated monomer (b-2) can improve the stability of the obtained water-dispersible hydroxyl group-containing acrylic resin (A1 ′) in an aqueous medium. Further, when a compound having reactivity with a hydroxyl group is used as the curing agent (B) described later, the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) and the curing agent (B) are cross-linked and excellent in water resistance. A coated film can be formed. As the hydroxyl group-containing polymerizable unsaturated monomer (b-2), those described above can be used.
  • Carboxyl group-containing polymerizable unsaturated monomer (b-3) can improve the stability of the obtained water-dispersible hydroxyl group-containing acrylic resin (A1 ′) in an aqueous medium.
  • a compound having reactivity with a carboxyl group is used as the curing agent (B) described later, the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) and the curing agent (B) are cross-linked, resulting in water resistance. An excellent coating film can be formed.
  • carboxyl group-containing polymerizable unsaturated monomer (b-3) examples include (meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate, and the like. These monomers can be used alone or in combination of two or more.
  • the carboxyl group-containing polymerizable unsaturated monomer (b-3) is acrylic acid and / or methacrylic acid. It is preferable that
  • Polymerizable unsaturated monomers (b-4) other than polymerizable unsaturated monomers (b-1) to (b-3) The monomer component (b) is added to the hydrophobic polymerizable unsaturated monomer (b-1), the hydroxyl group-containing polymerizable unsaturated monomer (b-2) and the carboxyl group-containing polymerizable unsaturated monomer (b-3), Further, if necessary, a polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-1) to (b-3) can be contained.
  • the polymerizable unsaturated monomer (b-4) can be appropriately selected and used depending on the properties desired for the water-dispersible hydroxyl group-containing acrylic resin (A1 ′). Specific examples of the polymerizable unsaturated monomer (b-4) are listed below. These can be used alone or in combination of two or more.
  • Examples of the polymerizable unsaturated monomer (b-4) include alkyl having 3 or less carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and the like.
  • (Meth) acrylate (meth) acrylonitrile, (meth) acrylamide, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, adduct of glycidyl (meth) acrylate and amine compound
  • Nitrogen-containing polymerizable unsaturated monomers such as allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate and other polymerizable unsaturated monomers having at least two polymerizable unsaturated groups in one molecule; glycidyl (Meta) a Relate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohex
  • the polymerizable unsaturated monomer (b-4) among the polymerizable unsaturated monomers (a1) to (a3) listed in the description of the polymerizable unsaturated monomer (a), the polymerizable unsaturated monomer (b Those not corresponding to -1) to (b-3) can also be used.
  • both the side chain of the copolymer and the hydroxyl group-containing acrylic resin (A1 ′) which is a film-forming resin both have a urea bond, a urethane bond, and / or an imide bond. Viscosity can be expected.
  • the hydrophobic polymerizable unsaturated monomer (b-1), the hydroxyl group-containing polymerizable unsaturated monomer (b-2), the carboxyl group-containing polymerizable unsaturated monomer (b-3) and the polymerizable property The content of the polymerizable unsaturated monomer (b-4) other than the unsaturated monomers (b-1) to (b-3) depends on the smoothness, sharpness, glitter and water resistance of the formed coating film. From the viewpoint, it is preferable to be within the following range based on the total mass of the monomer component (b).
  • the content ratio is based on the total mass of the monomer component (b). In the range of 1 to 70% by mass, preferably 1 to 50% by mass, more preferably 2 to 30% by mass.
  • the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) includes, for example, the hydrophobic polymerizable unsaturated monomer (b-1), the hydroxyl group-containing polymerizable unsaturated monomer (b-2), and the carboxyl group-containing polymerizable unsaturated monomer.
  • a monomer component (b) comprising a polymerizable unsaturated monomer (b-4) other than (b-3) and polymerizable unsaturated monomers (b-1) to (b-3) is obtained by a method known per se. It can be produced by copolymerization.
  • an emulsion polymerization method a method in which solution polymerization is performed in an organic solvent, and then the obtained copolymer is dispersed in water using a surfactant can be used.
  • emulsion polymerization is preferred from the viewpoint of improving the stability of the obtained water-dispersible hydroxyl group-containing acrylic resin (A1 ′) in an aqueous medium.
  • the emulsion polymerization method is usually a method in which a polymerizable unsaturated monomer that is insoluble or hardly soluble in water is polymerized in a state of being dispersed in water using a surfactant.
  • the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) prepared using the above (b-1) to (b-3) as a raw material has an acid value in the range of 1 to 100 mgKOH / g and a hydroxyl value of 1 to 1 It is preferably within the range of 100 mgKOH / g.
  • the acid value is more preferably 2 to 50 mgKOH / g from the viewpoint of storage stability of the paint, smoothness of the resulting coating film, sharpness, glitter and water resistance, and 5 to 30 mgKOH / g. More preferably, it is g.
  • the hydroxyl value is more preferably 2 to 80 mgKOH / g, and further preferably 5 to 60 mgKOH / g. .
  • the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) has a core / shell structure from the viewpoint of improving the stability of the obtained water-dispersible hydroxyl group-containing acrylic resin (A1 ′) in an aqueous medium.
  • the core part is preferably crosslinked.
  • the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) has a core / shell type structure, 0.1 to 30% by mass of a polymerizable unsaturated monomer and a polymerizable unsaturated group having a core part having at least two polymerizable unsaturated groups in one molecule based on the total mass of monomer components constituting the core part Is a copolymer (I) having 70 to 99.9% by mass of a polymerizable unsaturated monomer having 1 per molecule as a monomer component, and the total amount of monomer components constituting the core portion and the shell portion.
  • each monomer is 5 to 70% by mass of the hydrophobic polymerizable unsaturated monomer (b-1) based on the total mass of the monomer components constituting the core part and the shell part, and the hydroxyl group-containing polymerizable unsaturated monomer.
  • B-2) 0.1-2 % By weight, 0.1 to 20% by weight of the carboxyl group-containing polymerizable unsaturated monomer (b-3), polymerizable unsaturated monomers other than the polymerizable unsaturated monomers (b-1) to (b-3) (b -4)
  • a core-shell type water-dispersible acrylic resin (A1′-1) of 0 to 94.8% by mass is preferable.
  • a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups used as a monomer for the core copolymer (I) in one molecule
  • the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule has a function of imparting a crosslinked structure to the core copolymer (I).
  • the proportion of the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule can be appropriately determined according to the degree of crosslinking of the core copolymer (I).
  • the mass is preferably 0.5% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 7% by mass.
  • a polymerizable unsaturated monomer having one polymerizable unsaturated group in one molecule used as a monomer for the core copolymer (I) is A polymerizable unsaturated monomer copolymerizable with a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule.
  • polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule examples include, 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 acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl (
  • a polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule a polymerizable unsaturated monomer having a C 1 or 2 alkyl group may be used as at least a part thereof. preferable.
  • Examples of the polymerizable unsaturated monomer having an alkyl group having 1 or 2 carbon atoms include methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. These monomers can be used alone or in combination of two or more.
  • the alkyl group having 1 or 2 carbon atoms is The proportion of the polymerizable unsaturated monomer used is determined from the viewpoint of smoothness, sharpness and glitter of the resulting coating film, and the polymerizable unsaturated monomer and polymer having two or more polymerizable unsaturated groups in one molecule 20 to 99.9% by mass, preferably 30 to 99.5% by mass, more preferably 40 to 99% by mass, based on the total amount of polymerizable unsaturated monomers having one polymerizable unsaturated group per molecule It is preferable to be within the range.
  • the core-shell type water-dispersible acrylic resin (A1′-1) can generally have an average particle diameter in the range of about 10 to 1,000 nm, particularly about 20 to 500 nm.
  • the average particle size of the core-shell type water-dispersible acrylic resin (A1′-1) is diluted with deionized water by a conventional method using a dynamic light scattering particle size distribution analyzer. From the value measured at 20 ° C.
  • a dynamic light scattering particle size distribution measuring apparatus for example, “Submicron Particle Analyzer N5” (trade name, manufactured by Beckman Coulter, Inc.) can be used.
  • acid groups such as carboxyl groups of the water-dispersible acrylic resin are neutralized with a neutralizing agent.
  • the neutralizing agent is not particularly limited as long as it can neutralize an acid group.
  • sodium hydroxide, potassium hydroxide, trimethylamine, 2- (dimethylamino) ethanol, 2-amino-2-methyl- Examples include 1-propanol, triethylamine, aqueous ammonia, and the like. These neutralizing agents are desirably used in such an amount that the pH of the aqueous dispersion of the water-dispersible acrylic resin after neutralization becomes about 6.5 to 9.0.
  • the core-shell type water-dispersible acrylic resin (A1′-1) contains a polymerizable unsaturated group from the viewpoint of improving the smoothness, sharpness, glitter and water resistance of the coating film to be formed.
  • 0.1 to 30% by mass of a polymerizable unsaturated monomer having two or more in one molecule and 70 to 99.9% by mass of a polymerizable unsaturated monomer having one polymerizable unsaturated group in one molecule are monomer components.
  • a core part which is a copolymer (I), 5 to 80% by mass of a hydrophobic polymerizable unsaturated monomer (b-1), 0.1 to 50% by mass of a hydroxyl group-containing polymerizable unsaturated monomer (b-2) Carboxyl group-containing polymerizable unsaturated monomer (b-3) 0.1 to 50% by mass and polymerizable unsaturated monomers other than the polymerizable unsaturated monomers (b-1) to (b-3) (b-4) )
  • a core-shell type water-dispersible acrylic resin (A1′-2) within the range is preferable.
  • the ratio of copolymer (I) / copolymer (II) is 50 by solid content mass ratio from a viewpoint of the smoothness of a coating film to be formed, sharpness, brightness, and water resistance improving. / 50 to 85/15 is preferable, and about 65/35 to 80/20 is more preferable.
  • the use ratio of the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in the core portion in the molecule is the core portion copolymer.
  • the degree of crosslinking in (I) usually one polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule and one polymerizable unsaturated group in one molecule.
  • the amount is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 7% by mass, based on the total amount of polymerizable unsaturated monomers having. preferable.
  • the hydrophobic polymerizable unsaturated monomer (b-1), the hydroxyl group-containing polymerizable unsaturated monomer (b-2), and the carboxyl group-containing in the shell portion The content of the polymerizable unsaturated monomer (b-3) and the polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-1) to (b-3) is stable in an aqueous medium. From the viewpoint of excellent properties and smoothness, sharpness, glitter and water resistance of the resulting coating film, it is preferable to be within the following range on the basis of the total mass of the monomer components constituting the shell portion.
  • the content ratio is based on the total mass of the monomer component (b).
  • 1 is a polymerizable unsaturated group from the viewpoint of improving the smoothness, sharpness and glitter of the resulting coating film. It is preferable not to use a polymerizable unsaturated monomer having two or more in the molecule and to make the copolymer (II) uncrosslinked.
  • the core-shell type water-dispersible acrylic resin (A1′-2) includes, for example, 0.1 to 30% by mass of a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule, After emulsion polymerization of a monomer mixture composed of 70 to 99.9% by weight of a polymerizable unsaturated monomer having one saturated group per molecule to obtain an emulsion of the core copolymer (I), Hydrophobic polymerizable unsaturated monomer (b-1) 5 to 80% by mass, hydroxyl group-containing polymerizable unsaturated monomer (b-2) 0.1 to 50% by mass, carboxyl group-containing polymerizable unsaturated monomer (b-) 3) A monomer mixture comprising 0.1 to 50% by mass and 0 to 94.8% by mass of the polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-1) to (b-3). Is added, and emulsion
  • the emulsion polymerization for preparing an emulsion of the core copolymer (I) can be performed by a conventionally known method. For example, it can be carried out by emulsion polymerization of the monomer mixture using a polymerization initiator in the presence of a surfactant.
  • anionic surfactants and nonionic surfactants are suitable.
  • anionic surfactant include sodium salts and ammonium salts such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylphosphoric acid.
  • nonionic surfactants include polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonyl phenyl ether, Polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, etc. Is mentioned.
  • a reactive anionic surfactant having an unsaturated group can also be used. Of these, it is preferable to use a reactive anionic surfactant.
  • Examples of the reactive anionic surfactant include sodium salts of sulfonic acid compounds having radically polymerizable unsaturated groups such as allyl group, methallyl group, (meth) acryloyl group, propenyl group, butenyl group, An ammonium salt etc. can be mentioned.
  • an ammonium salt of a sulfonic acid compound having a radically polymerizable unsaturated group is preferable because the resulting coating film is excellent in water resistance.
  • Examples of commercially available ammonium salts of the sulfonic acid compound include “Latemul S-180A” (trade name, manufactured by Kao Corporation).
  • ammonium salts of sulfonic acid compounds having radically polymerizable unsaturated groups ammonium salts of sulfonic acid compounds having radically polymerizable unsaturated groups and polyoxyalkylene groups are more preferred.
  • examples of commercially available ammonium salts of sulfonic acid compounds having a radical polymerizable unsaturated group and a polyoxyalkylene group include “AQUALON KH-10” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Latemul PD- 104 "(trade name, manufactured by Kao Corporation),” ADEKA rear soap SR-1025 "(trade name, manufactured by ADEKA), and the like.
  • the amount of the surfactant used is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass, based on the total amount of all monomers used. preferable.
  • polymerization initiator examples include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxide.
  • Organic peroxides such as -2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile, Azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4'-azobis (4-cyano Tanic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis ⁇ 2-methyl-N- [2- (1-hydroxy Butyl)]-propionamide ⁇ and the like; and persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate.
  • persulfates such as potassium persulfate, ammoni
  • polymerization initiators can be used alone or in combination of two or more. Moreover, it is good also as a redox initiator by using together with reducing agents, such as saccharide
  • reducing agents such as saccharide
  • the amount of the polymerization initiator used is generally preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the total mass of all monomers used.
  • the method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be previously contained in the monomer mixture or the aqueous medium, or may be added all at once during the polymerization, or may be added dropwise.
  • the core-shell type water-dispersible acrylic resin (A1′-2) is prepared by adding a hydrophobic polymerizable unsaturated monomer (b-1) and a hydroxyl group-containing polymerizable polymer to the emulsion of the core copolymer (I) obtained above.
  • the monomer mixture forming the shell part copolymer (II) can appropriately contain components such as the polymerization initiator, chain transfer agent, reducing agent, and surfactant as required.
  • the monomer mixture can be dropped as it is, but it is desirable to drop the monomer mixture as a monomer emulsion obtained by dispersing the monomer mixture in an aqueous medium.
  • the particle size of the monomer emulsion is not particularly limited.
  • the monomer mixture or an emulsion thereof is dripped in a batch or gradually, and an emulsion of the core copolymer (I) is obtained. And a method of heating to an appropriate temperature while stirring.
  • the core-shell type water-dispersible acrylic resin (A1′-2) thus obtained has a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule and a polymerizable unsaturated group in one molecule.
  • Hydroxyl-containing polyester resin (A2) In the aqueous coating composition of the present invention, the coating film performance such as smoothness, sharpness, and water resistance of the coating film obtained by using the hydroxyl group-containing polyester resin (A2) as the film-forming resin (A). Can be improved.
  • the hydroxyl group-containing polyester resin (A2) can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component.
  • the acid component compounds usually used as an acid component in the production of a polyester resin can be used.
  • the acid component include an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, and the like.
  • the aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterified product of the aliphatic compound.
  • Examples of the aliphatic polybasic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, butane.
  • Examples thereof include aliphatic polycarboxylic acids such as tetracarboxylic acids; anhydrides of the aliphatic polyvalent carboxylic acids; and esterified products of lower alkyls having about 1 to 4 carbon atoms of the aliphatic polyvalent carboxylic acids.
  • the above aliphatic polybasic acids can be used alone or in combination of two or more.
  • aliphatic polybasic acid it is particularly preferable to use adipic acid and / or adipic acid anhydride from the viewpoints of smoothness and sharpness of the resulting coating film.
  • the alicyclic polybasic acid is generally a compound having one or more alicyclic structures and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and an esterified product of the compound.
  • the alicyclic structure is mainly a 4-6 membered ring structure.
  • Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl- Alicyclic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid; An anhydride of an alicyclic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to 4 carbon atoms of the alicyclic polyvalent carboxylic acid.
  • the said alicyclic polybasic acid can be used individually or in combination of 2 or more types.
  • Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, from the viewpoint of smoothness and sharpness of the resulting coating film. It is preferable to use an acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, and among them, 1,2-cyclohexanedicarboxylic acid and More preferably, 1,2-cyclohexanedicarboxylic anhydride is used.
  • the aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an esterified product of the aromatic compound, for example, phthalic acid , Isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, and other aromatic polycarboxylic acids; anhydrides of the aromatic polycarboxylic acids; Examples include esterified products of lower alkyl having about 1 to 4 carbon atoms of polyvalent carboxylic acids.
  • the aromatic polybasic acids can be used alone or in combination of two or more.
  • aromatic polybasic acid it is preferable to use phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, or trimellitic anhydride.
  • acid components other than the above-mentioned aliphatic polybasic acid, alicyclic polybasic acid and aromatic polybasic acid can also be used.
  • Such acid component is not particularly limited, for example, coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, Fatty acids such as castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane Acid, monocarboxylic acids such as 10-phenyloctadecanoic acid; and hydroxycarboxy
  • a polyhydric alcohol having two or more hydroxyl groups in one molecule can be preferably used.
  • the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl
  • alcohol components other than the above polyhydric alcohols can be used.
  • the alcohol component is not particularly limited, and examples thereof include monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, and 2-phenoxyethanol; propylene oxide, butylene oxide, “Cardura E10” (trade name, HEXION Specialty) Examples include alcohol compounds obtained by reacting monoepoxy compounds such as Chemicals, Inc. (glycidyl esters of synthetic highly branched saturated fatty acids) and acids.
  • the method for producing the hydroxyl group-containing polyester resin (A2) is not particularly limited, and can be performed according to a usual method.
  • the acid component and the alcohol component are heated in a nitrogen stream at about 150 to 250 ° C. for about 5 to 10 hours, and subjected to esterification reaction or transesterification reaction of the acid component and alcohol component, to form a hydroxyl group.
  • a containing polyester resin can be produced.
  • the acid component and the alcohol component When the acid component and the alcohol component are esterified or transesterified, they may be added to the reaction vessel at one time, or one or both may be added in several portions. . Moreover, after synthesizing a hydroxyl group-containing polyester resin, the resulting hydroxyl group-containing polyester resin may be reacted with an acid anhydride to be half-esterified to obtain a carboxyl group- and hydroxyl group-containing polyester resin. Moreover, after synthesizing a carboxyl group-containing polyester resin, the above alcohol component may be added to obtain a hydroxyl group-containing polyester resin.
  • dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl as a catalyst for promoting the reaction, dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl
  • a catalyst known per se, such as titanate can be used.
  • the hydroxyl group-containing polyester resin (A2) can be modified with a fatty acid, a monoepoxy compound, a polyisocyanate compound or the like during or after preparation of the resin.
  • fatty acid examples include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor Oil fatty acid, safflower oil fatty acid and the like can be mentioned.
  • “Cardura E10” (trade name, manufactured by HEXION Specialty Chemicals, glycidyl ester of synthetic highly branched saturated fatty acid) is preferably used. it can.
  • polyisocyanate compound examples include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, and methylcyclohexane-2.
  • 6-diisocyanate 4,4'-methylenebis (cyclohexylisocyanate), 1,3- (isocyanatomethyl) cyclohexane and other alicyclic diisocyanate compounds
  • aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate
  • Organic polyisocyanates such as polyisocyanates such as lysine triisocyanates and more Nate itself; adducts of these organic polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc .; cyclized polymers of these organic polyisocyanates (for example, isocyanurates), biuret type adducts Etc.
  • These polyisocyanate compounds can be used alone or in admixture of two or more.
  • the content of the alicyclic polybasic acid in the acid component of the raw material is selected from the viewpoint of excellent smoothness, sharpness and water resistance of the obtained coating film.
  • the amount is preferably about 20 to 100 mol%, more preferably about 25 to 95 mol%, still more preferably about 30 to 90 mol% based on the total amount of the components.
  • the alicyclic polybasic acid is 1,2-cyclohexanedicarboxylic acid and / or 1,2-cyclohexanedicarboxylic anhydride, from the viewpoint of excellent smoothness, sharpness, etc. of the resulting coating film Therefore, it is preferable.
  • the hydroxyl group-containing polyester resin (A2) preferably has a hydroxyl value of about 1 to 200 mgKOH / g, more preferably about 2 to 180 mgKOH / g, and still more preferably about 5 to 170 mgKOH / g.
  • its acid value is preferably about 5 to 150 mgKOH / g, more preferably about 10 to 100 mgKOH / g, More preferably, it is about 80 mgKOH / g.
  • the number average molecular weight of the hydroxyl group-containing polyester resin (A2) is preferably about 500 to 50,000, more preferably about 1,000 to 30,000, and about 1,200 to 10,000. More preferably.
  • the neutralization of the hydroxyl group-containing polyester resin (A2) can be performed using a basic compound.
  • the basic compound include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide; ammonia; ethylamine, propylamine, butylamine Primary monoamines such as benzylamine, monoethanolamine, 2,2-dimethyl-3-amino-1-propanol, 2-aminopropanol, 2-amino-2-methyl-1-propanol, 3-aminopropanol; Secondary monoamines such as diethylamine, diethanolamine, di-n-propanolamine, di-isopropanolamine, N-methylethanolamine, N-ethylethanolamine; dimethylethanolamine, trimethylamine, triethylamine, triisopropylamine Tertiary monoamines such as methyldiethanolamine and 2- (di
  • the amount of the hydroxyl group-containing polyester resin (A2) is usually 2 to 70 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the resin solid content in the paint. More preferably, it can be in the range of 15 to 40 parts by mass.
  • polyurethane resin examples include at least one diol selected from the group consisting of aliphatic and / or alicyclic diisocyanates, polyether diols, polyester diols, and polycarbonate diols, low molecular weight polyhydroxy compounds, and dimethylol alkanoic acids.
  • a urethane prepolymer is produced by reaction, neutralized with a tertiary amine, emulsified and dispersed in water, and then an aqueous solution containing a chain extender such as polyamine, a crosslinking agent and / or a terminator as necessary. Examples thereof include those obtained by mixing with a medium and reacting until the isocyanate group is substantially eliminated.
  • a self-emulsifying type polyurethane resin having an average particle diameter of about 0.001 to about 3 ⁇ m can be usually obtained.
  • the blending amount of the polyurethane resin in the aqueous coating composition of the present invention is usually 2 to 70 parts by weight, preferably 5 to 50 parts by weight, and more preferably based on 100 parts by weight of the resin solid content in the paint. It can be in the range of 8 to 30 parts by mass.
  • the curing agent (B) is a compound capable of curing the aqueous coating composition of the present invention by reacting with a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group in the film-forming resin (A).
  • the curing agent (B) include amino resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy group-containing compounds, carboxyl group-containing compounds, carbodiimide group-containing compounds, and the like. Of these, amino resins capable of reacting with hydroxyl groups, polyisocyanate compounds and blocked polyisocyanate compounds; carbodiimide group-containing compounds capable of reacting with carboxyl groups are preferred. Of these, amino resins and blocked polyisocyanate compounds are preferred, and amino resins are more preferred.
  • curing agent (B) can be used individually or in combination of 2 or more types.
  • the partial methylolation amino resin obtained by reaction of an amino component and an aldehyde component, or a complete methylolation amino resin can be used.
  • the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
  • the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
  • what methylated the methylol group of the said methylolated amino resin partially or completely with suitable alcohol can also be used.
  • Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
  • Melamine resin is preferred as the amino resin.
  • methyl ether melamine resins in which methylol groups of partially or fully methylolated melamine resins are partially or completely etherified with methyl alcohol, methylol groups of partially or fully methylolated melamine resins are partially or completely with butyl alcohol.
  • Preferred is a methyl-butyl mixed etherified melamine resin in which the methylol group of a partially or fully methylolated melamine resin is partially or completely etherified with methyl alcohol and butyl alcohol.
  • Etherified melamine resins are more preferred.
  • the melamine resin preferably has a weight average molecular weight of about 400 to 6,000, more preferably about 800 to 5,000, and still more preferably about 1,000 to 4,000. The most preferred range is about 1,200 to 3,000.
  • the number-average molecular weight and the weight-average molecular weight of the film-forming resin (A) and the curing agent (B) are measured using a gel permeation chromatograph (GPC). Is a value obtained by converting the molecular weight of polystyrene based on the retention time (retention capacity) of standard polystyrene having a known molecular weight measured under the same conditions.
  • GPC gel permeation chromatograph
  • G2000HXL (trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.
  • melamine resin Commercially available products can be used as the melamine resin.
  • Examples of commercially available product names include “Cymel 202”, “Cymel 203”, “Cymel 238”, “Cymel 251”, “Cymel 303”, “Cymel 323”, “Cymel 324”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 385”, “Cymel 1156”, “Cymel 1158”, “Cymel 1116”, “Cymel 1130” (above, made by Nippon Cytec Industries, Inc.), “Uban 120”, “ Examples include “Uban 20HS”, “Uban 20SE60”, “Uban 2021”, “Uban 2028”, “Uban 28-60” (all manufactured by Mitsui Chemicals, Inc.).
  • a hydroxyl group-containing acrylic resin (A1) such as a core-shell type water-dispersible hydroxyl group-containing acrylic resin (A1′-1) is used as the film-forming resin (A).
  • the curing agent (B) it is possible to use a melamine resin having a weight average molecular weight of about 1,000 to 4,000, particularly about 1,200 to 3,000. From the viewpoint of excellent properties, it is preferable.
  • a sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid; monobutyl phosphoric acid, dibutyl phosphoric acid, mono 2-ethylhexyl phosphoric acid, Alkyl phosphate esters such as di-2-ethylhexyl phosphate; salts of these acids with amine compounds and the like can be used as catalysts.
  • the blocked polyisocyanate compound is a compound obtained by blocking an isocyanate group of a polyisocyanate compound having at least two isocyanate groups in one molecule with a blocking agent.
  • the blocking agent include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and hydroxybenzoic acid methyl; ⁇ -caprolactam, ⁇ -valerolactam, Lactams such as ⁇ -butyrolactam and ⁇ -propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl
  • Acid amides succinimides, phthalic imides, maleic imides and other imides; diphenylamines, phenylnaphthylamines, xylidines, N-phenylxylidines, carbazoles, anilines, naphthylamines, butylamines, dibutylamines, butylphenylamines and other amines Imidazole, imidazole such as 2-ethylimidazole; urea, thiourea, ethyleneurea, ethylenethiourea, diphenylurea N- phenylcarbamate ester of carbamic acid such as phenyl; ethyleneimine, imine and propylene imine; urea in sodium bisulfite, sulfite, such as bisulfite potassium; compounds such azole systems.
  • azole compounds examples include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; Imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; 2-methylimidazoline And imidazoline derivatives such as 2-phenylimidazoline.
  • polyisocyanate compound having at least two isocyanate groups in one molecule examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; hydrogenated xylylene diisocyanate, cyclohexane.
  • Alicyclic diisocyanate compounds such as silylene diisocyanate and isophorone diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate; 2-isocyanate Natoethyl-2,6-diisocyanatocaproe Tri- or higher valent organic polyisocyanate compounds such as 3-isocyanatomethyl-1,6-hexamethylene diisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (commonly known as triaminononane triisocyanate); And dimers or trimers of the polyisocyanate compound: a prepolymer obtained by subjecting these polyisocyanate compound and polyhydric alcohol, low mo
  • the carbodiimide group-containing compound for example, a compound obtained by decarbonizing the isocyanate groups of the polyisocyanate compound can be used.
  • the carbodiimide group-containing compound it is preferable to use a polycarbodiimide compound having at least two carbodiimide groups in one molecule.
  • the polycarbodiimide compound it is preferable to use a water-soluble or water-dispersible polycarbodiimide compound from the viewpoints of smoothness and sharpness of the resulting coating film.
  • a water-soluble or water-dispersible polycarbodiimide compound any polycarbodiimide compound that can be stably dissolved or dispersed in an aqueous medium can be used without particular limitation.
  • water-soluble polycarbodiimide compound examples include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L2”, and “Carbodilite V-04” (all manufactured by Nisshinbo Co., Ltd.). , Product name), etc. can be used.
  • water-dispersible polycarbodiimide compound examples include “Carbodilite E-01”, “Carbodilite E-02” (both manufactured by Nisshinbo Co., Ltd.), and the like.
  • the above polycarbodiimide compounds can be used alone or in combination of two or more.
  • the blending ratio of the film-forming resin (A) and the curing agent (B) in the aqueous coating composition according to the present invention is the sum of both from the viewpoints of smoothness of the coating film, sharpness, and water resistance improvement.
  • the former is about 30 to 95% by mass, preferably about 50 to 90% by mass, more preferably about 60 to 80% by mass, and the latter is about 5 to 70% by mass, preferably 10 to 50% by mass. It is preferable that the amount is about 20 to 40% by mass.
  • the curing agent (B) is usually in the range of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the resin solid content in the paint. It can mix
  • the amount of the hydroxyl group-containing acrylic resin (A1) is the total solid content of the film-forming resin (A) and the curing agent (B).
  • the amount is preferably from about 2 to 70% by mass, more preferably from about 5 to 55% by mass, and still more preferably from about 10 to 40% by mass.
  • the amount of the hydroxyl group-containing polyester resin (A2) is the sum of the film-forming resin (A) and the curing agent (B).
  • the solid content is preferably about 2 to 70% by mass, more preferably about 5 to 55% by mass, and still more preferably about 10 to 40% by mass.
  • the aqueous coating composition according to the present invention is, for example, a known method using the film-forming resin (A) and the copolymer, and optionally the curing agent (B).
  • aqueous medium examples include water or a water-organic solvent mixed solution obtained by dissolving a hydrophilic organic solvent in water.
  • the hydrophilic organic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Examples thereof include butyl ether, tripropylene glycol monomethyl ether, and 3-methyl 3-methoxybutanol, and these can be used alone or in admixture of two or more.
  • the mixing ratio of water and the organic solvent is not particularly limited, but the content of the organic solvent is about 1 to 50% by mass, preferably about 5 to 35% by mass of the mixed solution. Preferably it is.
  • the water-based paint is a term contrasted with an organic solvent-type paint, and generally, a film-forming resin, a pigment, and the like are dispersed and / or dispersed in water or a medium mainly containing water (aqueous medium). It means dissolved paint.
  • the coating composition of the present invention is a water-based coating
  • the water content in the coating composition is in the range of 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 70% by mass. It is preferable that
  • the blending ratio of the film-forming resin (A) and the copolymer is determined based on the storage stability of the aqueous coating composition, the appearance of the formed coating film, and the coating film performance (water resistance).
  • Etc. from the viewpoint of 100 parts by weight of the film-forming resin (A), the amount of the copolymer is 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably It is preferably within the range of 0.2 to 10 parts by mass.
  • the amount of the copolymer is determined from the viewpoints of storage stability of the aqueous coating composition, appearance of the formed coating film, coating film performance (water resistance, etc.), and the like.
  • the amount is preferably 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the aqueous coating composition.
  • the aqueous coating composition of the present invention contains the copolymer and the water-dispersible hydroxyl group-containing acrylic resin (A1).
  • ') Can be contained in an amount within the range described below on the basis of 100 parts by mass of the resin solid content in the aqueous coating composition.
  • Copolymer 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass
  • the resin solid content in the aqueous coating composition is usually the resin solid content of the copolymer and the water-dispersible hydroxyl group-containing acrylic resin (A1 ′) and, if necessary, the aqueous coating composition of the present invention. It is the total of other resin and solid content of the curing agent (B) added to the product.
  • the water-based coating composition of the present invention may further include a glitter pigment, a colored pigment, an extender pigment, a hydrophobic organic solvent, a curing catalyst, an ultraviolet absorber, a light stabilizer, a pigment dispersant, an antifoaming agent, if necessary.
  • Additives for coating materials such as plasticizers, surface conditioners, anti-settling agents and the like can be contained.
  • the bright pigment examples include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide coated with titanium oxide or iron oxide. And mica. These glitter pigments can be used alone or in combination of two or more. These glitter pigments are preferably in the form of flakes.
  • aluminum, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide is preferable, and aluminum is more preferable.
  • the flake-like glitter pigment has a longitudinal dimension of usually about 1 to 100 ⁇ m, preferably about 5 to 40 ⁇ m, and a thickness of usually about 0.001 to 5 ⁇ m, preferably about 0.01 to 2 ⁇ m. Can be suitably used.
  • the aqueous coating composition of the present invention has the advantage that when it contains the above-mentioned glitter pigment, it can form a coating film having high flip-flop properties and excellent glitter with suppressed metallic unevenness.
  • the blending amount of the glittering pigment is usually 1 to 100 masses as solid content with respect to 100 mass parts of the film-forming resin (A). Preferably about 2 to 50 parts by weight, more preferably about 3 to 30 parts by weight.
  • the aqueous coating composition of the present invention can further contain a phosphate group-containing resin as a resin component in addition to the film-forming resin (A).
  • a phosphate group-containing resin as a resin component in addition to the film-forming resin (A).
  • the aqueous coating composition of the present invention contains the above-mentioned glitter pigment, particularly an aluminum pigment
  • the aqueous coating composition of the present invention provides smoothness, sharpness, metallic unevenness suppression of the obtained coating film, and From the viewpoint of water resistance, it is preferable to contain a phosphate group-containing resin.
  • the phosphate group-containing resin can be produced, for example, by copolymerizing a phosphate group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers by a known method such as a solution polymerization method.
  • a phosphate group-containing polymerizable unsaturated monomer examples include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, a reaction product of glycidyl (meth) acrylate and alkyl phosphoric acid, and the like. . These can be used alone or in combination of two or more.
  • the use ratio when copolymerizing the phosphoric acid group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer is 1/99 to 40 / in mass ratio of the former / the latter.
  • About 60 is preferable, about 5/95 to 35/65 is more preferable, and about 10/90 to 30/70 is further preferable.
  • the amount of the phosphate group-containing resin is usually 0.5 to 100 parts by mass with respect to 100 parts by mass of the film-forming resin (A). About 15 parts by mass is preferable, about 0.75 to 10 parts by mass is more preferable, and about 1 to 5 parts by mass is still more preferable.
  • color pigment examples include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. , Dioxazine pigments, diketopyrrolopyrrole pigments, and the like. These color pigments can be used alone or in combination of two or more.
  • the amount of the color pigment is usually about 1 to 200 parts by mass with respect to 100 parts by mass of the film-forming resin (A) as a solid content. It is preferably about 2 to 50 parts by mass, more preferably about 3 to 30 parts by mass.
  • extender pigment examples include talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, silica, and alumina white.
  • the amount of the extender is usually about 1 to 200 parts by mass with respect to 100 parts by mass of the film-forming resin (A) as a solid content. It is preferably about 2 to 50 parts by mass, more preferably about 3 to 30 parts by mass.
  • an organic solvent having a mass dissolved in 100 g of water at 20 ° C. of 10 g or less, preferably 5 g or less, more preferably 1 g or less can be used.
  • organic solvents include hydrocarbon solvents such as rubber volatile oil, mineral spirits, toluene, xylene, and solvent naphtha; 1-hexanol, 1-octanol, 2-octanol, 2-ethylhexanol, 1-decanol, benzyl Alcohols such as alcohol, ethylene glycol mono-2-ethylhexyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol mono 2-ethylhexyl ether, propylene glycol monophenyl ether Solvent; ester solvents such as n-butyl a
  • the above-mentioned hydrophobic organic solvent is preferably an alcohol-based hydrophobic organic solvent, more preferably an alcohol-based hydrophobic organic solvent having 7 to 14 carbon atoms, from the viewpoint of excellent glitter of the resulting coating film.
  • Alcohol-based hydrophobic organic solvents are preferable, and 2-ethyl-1-hexanol and / or ethylene glycol mono 2-ethylhexyl ether is more preferable.
  • the amount of the hydrophobic organic solvent is 10 to 100 parts by mass based on 100 parts by mass of the solid content in the aqueous coating composition.
  • the amount is preferably about 15 to 80 parts by mass, more preferably about 20 to 60 parts by mass.
  • the solid content of the aqueous coating composition of the present invention is usually preferably about 5 to 70% by mass, more preferably about 15 to 45% by mass, and further about 20 to 35% by mass. preferable.
  • the aqueous coating composition of the present invention the change smoothness of the resulting coating film, distinctness of image, from the viewpoint of excellent luster, at a measurement temperature of 20 ° C., a shear rate of from 0.0001Sec -1 to 10,000Sec -1 It is preferable that the viscosity V 1 at 1,000 sec ⁇ 1 is 0.1 Pa ⁇ sec or less, preferably 0.01 to 0.1 Pa ⁇ sec.
  • the aqueous coating composition of the present invention the smoothness of the resulting coating film, distinctness of image, from the viewpoint of excellent luster, at a measurement temperature of 20 °C, 10,000sec shear rate from 0.0001sec -1 -1 It is preferable that the viscosity V 2 at 0.1 sec ⁇ 1 in the range of 30 to 100 Pa ⁇ sec, preferably in the range of 35 to 70 Pa ⁇ sec.
  • the viscosity V 1 and the viscosity V 2 is able to use a viscoelasticity measuring apparatus measures.
  • a viscoelasticity measuring apparatus for example, “HAAKE RheoStress RS150” (trade name, manufactured by HAAKE) or the like can be used.
  • the aqueous coating composition containing the copolymer of the present invention has a viscosity characteristic in which the viscosity is high and the viscosity decreases as the shear rate increases.
  • the aqueous coating composition contains a surfactant. Even in the case where it is contained, the reason is that the polymer present in the side chain of the copolymer of the present invention is a urea bond and / or urethane because it exhibits viscosity and decreases with increasing shear rate. Since it has a bond, a network structure to which a hydrogen bond contributes is formed and a high viscosity is developed.
  • the number average molecular weight of the polymer is in the range of 1,000 to 10,000, and a relatively large volume is obtained. Therefore, it is presumed that the network structure is hardly influenced by the surfactant.
  • the aqueous coating composition contains a resin having an ester bond as the film-forming resin (A), the polymerizable unsaturated monomer (a1) having a urea bond present in the side chain of the copolymer of the present invention.
  • the water-based coating composition of the present invention can form a coating film having an excellent appearance by coating on various objects.
  • the article to be coated to which the aqueous coating composition of the present invention is applied is not particularly limited.
  • the article to be coated include an outer plate portion of an automobile body such as a passenger car, a truck, a motorcycle, and a bus; an automobile component; an outer plate portion of a household electric product such as a mobile phone and an audio device.
  • the outer plate portion of the automobile body and the automobile parts are preferable.
  • the material of these objects to be coated is not particularly limited.
  • metal materials such as iron, aluminum, brass, copper, tinplate, stainless steel, galvanized steel, zinc alloy (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; Examples thereof include fiber materials such as paper and cloth. Of these, metal materials and plastic materials are preferred.
  • the object to be coated may be a metal surface of the metal material or a vehicle body formed from the metal material, and may be subjected to surface treatment such as phosphate treatment, chromate treatment, complex oxide treatment, A coating film may be formed thereon.
  • the undercoat coating film is preferably a coating film formed of an electrodeposition paint, preferably a cationic electrodeposition paint.
  • the desired coating film can be formed by curing the wet coating film.
  • the coating method of the aqueous coating composition of the present invention is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like. Can be formed. Of these, air spray coating or rotary atomization coating is preferred from the viewpoint of improving the smoothness, sharpness and flip-flop properties of the resulting coating film and suppressing metallic unevenness. Moreover, you may apply electrostatic at the time of coating as needed.
  • the coating amount of the aqueous coating composition of the present invention is such that the cured film thickness is usually about 1 to 50 ⁇ m, preferably about 3 to 50 ⁇ m, more preferably about 5 to 35 ⁇ m, and still more preferably about 8 to 25 ⁇ m. Preferably there is.
  • the wet coating film can be cured by applying the water-based coating composition of the present invention to the object to be coated and then heating it.
  • Heating can be performed by a known heating means.
  • a drying furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace can be used.
  • the heating temperature is preferably about 80 to 180 ° C, more preferably about 100 to 170 ° C, and further preferably about 120 to 160 ° C.
  • the heating time is not particularly limited, but is usually preferably about 10 to 60 minutes, more preferably about 20 to 40 minutes.
  • the preheating temperature is preferably about 40 to 100 ° C., more preferably about 50 to 90 ° C., and further preferably about 60 to 80 ° C.
  • the preheating time is preferably about 30 seconds to 15 minutes, more preferably about 1 to 10 minutes, and further preferably about 2 to 5 minutes.
  • the air blow can be usually performed by blowing air heated to a normal temperature or a temperature of about 25 ° C. to 80 ° C. for about 30 seconds to 15 minutes on the surface to be coated.
  • the water-based coating composition of the present invention forms a multilayer coating film comprising a base coat film and a clear coat film on an article to be coated such as an automobile body by a 2-coat 1-bake method, It can be used suitably.
  • the coating film formation method in this case can be performed according to the following method I.
  • Method I A step of forming a base coat film by applying the aqueous coating composition of the present invention to an object to be coated; (2) a step of applying a clear coat coating composition on the uncured base coat film to form a clear coat film; and (3) the uncured base coat film and the uncured clear coat film.
  • a method for forming a multilayer coating film comprising a step of heating the coating film to simultaneously cure both coating films.
  • the object to be coated in Method I is preferably an automobile body with an undercoat film, an automobile body with an undercoat film and an intermediate coat film, and the like.
  • the undercoat coating film is preferably a coating film formed of an electrodeposition coating, and more preferably a coating formed of a cationic electrodeposition coating.
  • the cured coating is a cured and dried state specified in JIS K 5600-1-1 (2004), that is, the center of the coating surface is strongly sandwiched between the thumb and index finger, and the coating surface is dented by a fingerprint. It is a coating film in which the movement of the coating film is not felt, the center of the coating surface is rapidly rubbed with a fingertip, and the coating surface is not rubbed.
  • the uncured coating film is a state in which the coating film has not reached the above-mentioned cured and dried state, and includes a dry-to-touch state and a semi-cured and dried state defined in JIS K 5600-1-1.
  • the coating film thickness is preferably about 3 to 40 ⁇ m, more preferably about 5 to 30 ⁇ m, more preferably 8 to 8 ⁇ m. It is more preferably about ⁇ 25 ⁇ m, and particularly preferably about 10 to 18 ⁇ m.
  • the coating thickness of the clear coat coating composition is preferably about 10 to 80 ⁇ m, more preferably about 15 to 60 ⁇ m, and still more preferably about 20 to 45 ⁇ m as a cured film thickness.
  • the above-mentioned preheating, air blowing, etc. are performed under heating conditions in which the coating film is not substantially cured. Is preferred. Further, after the application of the clear coat coating composition, if necessary, an interval of about 1 to 60 minutes can be provided at room temperature, or preheating can be performed at about 40 to 80 ° C. for about 1 to 60 minutes.
  • Curing of the water-based paint composition and the clear coat paint composition can be performed by the known heating means described above.
  • the heating temperature is preferably about 80 to 180 ° C, more preferably about 100 to 170 ° C, and further preferably about 120 to 160 ° C.
  • the heating time is preferably about 10 to 60 minutes, more preferably about 20 to 40 minutes. By this heating, both the base coat and the clear coat can be cured simultaneously.
  • the water-based coating composition of the present invention is a three-coat one-bake method in which a multilayer coating film composed of a first colored coating film, a second colored coating film, and a clear coating film is applied to an object such as an automobile body.
  • a multilayer coating film composed of a first colored coating film, a second colored coating film, and a clear coating film is applied to an object such as an automobile body.
  • it can be suitably used for forming the second colored coating film.
  • the coating film formation method in this case can be performed according to the following method II.
  • Method II (1) A step of forming a first colored coating film by applying a first colored coating composition to an object to be coated; (2) A step of forming the second colored coating film by coating the aqueous coating composition of the present invention on the uncured first colored coating film, (3) a step of applying a clear coat coating composition on the uncured second colored coating film to form a clear coat coating; and (4) the uncured first colored coating film, uncured
  • a method for forming a multilayer coating film comprising a step of simultaneously heating and curing a second colored coating film and an uncured clear coat film.
  • the method II is a method in which the coating method of the method I is performed on an uncured first colored coating film.
  • an automobile body or the like on which an undercoat film is formed is preferable.
  • the undercoat coating film is preferably formed of an electrodeposition paint, and more preferably formed of a cationic electrodeposition paint.
  • the coating thickness of the first colored coating composition is usually preferably about 3 to 50 ⁇ m, more preferably about 5 to 30 ⁇ m, and further preferably about 10 to 25 ⁇ m as a cured film thickness.
  • the coating thickness of the aqueous coating composition of the present invention is preferably about 1 to 30 ⁇ m, more preferably about 3 to 25 ⁇ m, and still more preferably about 5 to 20 ⁇ m as a cured film thickness.
  • the coating film thickness of the clear coat coating composition is usually preferably about 10 to 80 ⁇ m, more preferably about 15 to 60 ⁇ m, and further preferably about 20 to 45 ⁇ m in terms of cured film thickness.
  • method II include the following method II-1 and method II-2.
  • Method II-1 A step of applying a surface treatment to the steel sheet as necessary, coating an electrodeposition paint thereon, and curing it by heating to form a cured electrodeposition coating film; (2) In the intermediate coating booth, a step of coating the first colored coating composition on the cured electrodeposition coating film obtained in step (1) to form an intermediate coating film; (3) In the base coat painting booth, a step of coating the aqueous coating composition of the present invention on the uncured intermediate coating film obtained in step (2) to form a base coat; (4) In the clear coat coating booth, a step of forming a clear coat film by applying a clear coat paint on the base coat coated surface obtained in step (3); and (5) steps (2) to (4) A method for forming a multilayer coating film comprising the step of simultaneously curing the three coating films by heating the intermediate coating film, base coat and clear coat formed in (1).
  • the booth is a facility for maintaining the coating environment such as temperature and humidity within a certain range in order to ensure uniform coating quality, and is usually divided according to the type of paint to be painted.
  • the same paint may be applied twice in order to prevent sagging or unevenness of the paint applied to the object.
  • the first painting is called the first stage painting
  • the second painting is called the second stage painting.
  • the coating thickness of the first colored coating composition is usually preferably about 5 to 50 ⁇ m, more preferably about 10 to 30 ⁇ m, and still more preferably about 15 to 25 ⁇ m as a cured film thickness.
  • the coating film thickness of the aqueous coating composition of the present invention is preferably about 3 to 30 ⁇ m, more preferably about 5 to 25 ⁇ m, further preferably about 8 to 20 ⁇ m, and more preferably about 9 to 16 ⁇ m as a cured film thickness.
  • the coating thickness of the clear coat coating composition is usually preferably about 10 to 80 ⁇ m, more preferably about 15 to 60 ⁇ m, and further preferably about 20 to 45 ⁇ m in terms of cured film thickness.
  • the above method II-1 when an aqueous first colored coating composition is used as the first colored coating composition, after coating of the aqueous first colored coating composition, coating defects such as armpits are generated. From the viewpoint of prevention, it is preferable to perform the above-described preheating, air blowing, or the like under heating conditions in which the coating film is not substantially cured.
  • Method II-2 (1) A step of applying a surface treatment to the steel sheet as necessary, coating an electrodeposition paint thereon, and curing it by heating to form a cured electrodeposition coating film; (2) In the first stage of the base coat painting booth, a step of coating the first base coat paint on the cured electrodeposition paint film obtained in step (1) to form the first base coat paint film; (3) In the second stage of the base coat painting booth, a step of coating the aqueous base coating composition of the present invention on the first base coat film obtained in step (2) to form a second base coat film; (4) In the clear coat coating booth, a step of coating the second base coat film obtained in step (3) with a clear coat paint to form a clear coat film; and (5) steps (2) to A step of simultaneously curing these three coating films by heating the first base coat film, the second base coat film and the clear coat film formed in (4), A method for forming a multilayer coating film comprising:
  • the coating thickness of the first colored coating composition is usually about 3 to 40 ⁇ m, more preferably about 5 to 25 ⁇ m, and still more preferably about 10 to 20 ⁇ m in terms of cured film thickness.
  • the coating thickness of the aqueous coating composition of the present invention is preferably about 1 to 25 ⁇ m, more preferably about 3 to 20 ⁇ m, and still more preferably about 5 to 15 ⁇ m as a cured film thickness.
  • the coating thickness of the clear coat coating composition is usually preferably about 10 to 80 ⁇ m, more preferably about 15 to 60 ⁇ m, and still more preferably about 20 to 45 ⁇ m in terms of cured film thickness.
  • the coating method of the above method II-2 has an advantage that energy for adjusting the temperature and humidity of the intermediate coating booth can be reduced because the intermediate coating booth is unnecessary.
  • the first colored coating composition and the aqueous coating composition of the present invention are applied at the base coat coating booth, the first colored coating composition and the present invention are usually applied.
  • the heating device is not installed during the application of the aqueous coating composition, and the above-mentioned preheating is generally not performed on the first base coat film formed by applying the first colored coating composition.
  • the method II-2 has an advantage that energy for preheating can be reduced. Therefore, from the viewpoint of energy saving, in the coating method of Method II-2, it is preferable not to include a heating step between the coating of the first colored coating composition and the coating of the aqueous coating composition of the present invention.
  • the above-mentioned preheating, air blowing, etc. are performed under heating conditions in which the coating film is not substantially cured. Preferably it is done. Further, after the application of the clear coat coating composition, if necessary, an interval of about 1 to 60 minutes can be provided at room temperature, or preheating can be performed at about 40 to 80 ° C. for about 1 to 60 minutes.
  • Heat curing of the three-layer coating film of the uncured first colored coating film, the uncured second colored coating film, and the uncured clear coat film can be performed by the known heating means described above.
  • the heating temperature is preferably about 80 to 180 ° C, more preferably about 100 to 170 ° C, and further preferably about 120 to 160 ° C.
  • the heating time is preferably about 10 to 60 minutes, more preferably about 20 to 40 minutes.
  • thermosetting clear coat coating compositions for coating automobile bodies can be used.
  • examples thereof include an organic solvent-type thermosetting coating composition, a water-based thermosetting coating composition, and a powder thermosetting coating composition containing a base resin having a crosslinkable functional group and a crosslinking agent.
  • Examples of the crosslinkable functional group possessed by the base resin include a carboxyl group, a hydroxyl group, an epoxy group, and a silanol group.
  • Examples of the base resin include acrylic resin, polyester resin, alkyd resin, urethane resin, epoxy resin, and fluororesin.
  • Examples of the crosslinking 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.
  • the base resin / crosslinking agent combination of the clear coat coating composition includes 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. are preferred.
  • the clear coat coating composition may be a one-component paint or a multi-component paint such as a two-component urethane resin paint.
  • the clear coat coating composition may contain, if necessary, a coloring pigment, a bright pigment, a dye, and the like to such an extent that transparency is not hindered, and further an extender pigment, an ultraviolet absorber, and a light stabilizer.
  • a coloring pigment e
  • thermosetting intermediate coating composition can be used in the method II-1, and a known coating composition in the method II-2.
  • a thermosetting basecoat coating composition can be used.
  • a thermosetting coating composition containing a base resin having a crosslinkable functional group, a crosslinker, a color pigment, and an extender pigment can be suitably used.
  • Examples of the crosslinkable functional group possessed by the base resin include a carboxyl group, a hydroxyl group, and an epoxy group.
  • Examples of the base resin include acrylic resin, polyester resin, alkyd resin, and urethane resin.
  • Examples of the crosslinking agent include melamine resin, polyisocyanate compound, blocked polyisocyanate compound and the like.
  • any of an organic solvent-type coating composition, an aqueous coating composition, and a powder coating composition may be used. Of these, it is preferable to use an aqueous coating composition.
  • the first colored coating composition and the clear coat coating composition can be applied by a known method such as air spray coating, airless spray coating, or rotary atomization coating. .
  • Production and production example 1 of polymerizable unsaturated monomer (a1) having urea bond A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser and dropping device was charged with 40 parts of tetrahydrofuran and 52.9 parts of 2-methacryloyloxyethyl isocyanate, and the temperature was lowered to 15 ° C. Next, 37 parts of a 37.8% methanol solution of ethylamine was added dropwise over 1 hour while stirring at 15 ° C., and after completion of the addition, the mixture was aged by stirring at room temperature for 2 hours.
  • the temperature is raised to 60 ° C., and the solvent is removed under reduced pressure to thereby remove a polymerizable unsaturated monomer having a urea bond (a1-1) (2- (3-ethylureido) ethyl methacrylate, active ingredient 100%) Got.
  • the polymerizable unsaturated monomer (a1-1) having a urea bond has an ethylurea group.
  • Production Example 2 A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 40 parts of tetrahydrofuran and 51.2 parts of 2-methacryloyloxyethyl isocyanate, and the temperature was raised to 35 ° C. Next, 24.1 parts of butylamine was added dropwise over 1 hour with stirring while maintaining 35 ° C. After completion of the dropwise addition, the mixture was aged by stirring at 35 ° C for 2 hours.
  • a polymerizable unsaturated monomer having a urea bond (a1-2) (2- (3-butylureido) ethyl methacrylate, active ingredient 100%) Got.
  • the polymerizable unsaturated monomer (a1-2) having a urea bond has a butylurea group.
  • Production Example 3 A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 40 parts of tetrahydrofuran and 51.2 parts of 2-methacryloyloxyethyl isocyanate, and the temperature was raised to 35 ° C. Next, 19.5 parts of isopropylamine was added dropwise over 1 hour with stirring while maintaining 35 ° C. After completion of the dropwise addition, the mixture was aged by stirring at 35 ° C for 2 hours.
  • a polymerizable unsaturated monomer having a urea bond (a1-3) (2- (3-isopropylureido) ethyl methacrylate, active ingredient 100%) Got.
  • the polymerizable unsaturated monomer (a1-3) having a urea bond has an isopropyl urea group.
  • Production Example 4 A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 40 parts of tetrahydrofuran and 51.2 parts of 2-methacryloyloxyethyl isocyanate, and the temperature was raised to 35 ° C. Next, while maintaining at 35 ° C., 42.6 parts of 2-ethylhexylamine was added dropwise over 1 hour with stirring, and after completion of the dropwise addition, aging was performed by stirring at 35 ° C. for 2 hours.
  • the temperature is raised to 60 ° C., and the solvent is removed under reduced pressure, whereby a polymerizable unsaturated monomer having a urea bond (a1-4) (2- [3- (2-ethylhexyl) ureido] ethyl methacrylate, effective 100% component) was obtained.
  • the polymerizable unsaturated monomer (a1-4) having a urea bond has a 2-ethylhexylurea group.
  • Production Example 5 A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 40 parts of tetrahydrofuran and 51.2 parts of 2-methacryloyloxyethyl isocyanate, and the temperature was raised to 35 ° C. Next, 24.1 parts of diethylamine was added dropwise over 1 hour with stirring while maintaining 35 ° C. After completion of the dropwise addition, the mixture was aged by stirring at 35 ° C for 2 hours.
  • a polymerizable unsaturated monomer having a urea bond (a1-5) (2- (3,3-diethylureido) ethyl methacrylate, active ingredient 100 %).
  • the polymerizable unsaturated monomer (a1-5) having a urea bond has a diethylurea group.
  • Production Example 6 A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, air inlet tube, drying tube and dropping device was charged with 42.9 parts of 2-hydroxyethyl methacrylate and 0.039 parts of p-methoxyphenol and dried. The temperature was raised to 60 ° C. while introducing air at 20 mL per minute. Next, while maintaining 60 ° C., 66.6 parts of isophorone diisocyanate was added dropwise over 1 hour while stirring and introducing dry air. After completion of the dropwise addition, the mixture was aged by stirring at 60 ° C. for 2 hours. . Next, the temperature was raised to 80 ° C., and the mixture was further aged at the same temperature for 1 hour for aging.
  • a polymerizable unsaturated monomer having a urea bond (a1-6) (2- ⁇ [5- (3-butylureido) -1,3 , 3-Trimethylcyclohexyl] methylcarbamoyloxy ⁇ ethyl methacrylate and 2- ⁇ 3-[(3-butylureido) methyl] -3,5,5-trimethylcyclohexylmethylcarbamoyloxy ⁇ ethyl methacrylate, active ingredient 100% )
  • the polymerizable unsaturated monomer (a1-6) having a urea bond has a butylurea group and a urethane bond.
  • Production and production example 7 of polymerizable unsaturated monomer (a2) having urethane bond Into a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, air introduction tube, drying tube and dropping device, 67.7 parts of 2-methacryloyloxyethyl isocyanate and 0.40 part of p-methoxyphenol were charged, The temperature was raised to 50 ° C. while introducing dry air at 20 mL / min. Next, 32.3 parts of butanol was added dropwise over 1 hour while stirring and introducing dry air while maintaining 50 ° C. After completion of the dropping, the temperature was raised to 60 ° C., and the mixture was aged by stirring at the same temperature for 1 hour.
  • a polymerizable unsaturated monomer having a urethane bond (a2-1) (2- (butoxycarbonylamino) ethyl methacrylate, active ingredient 100% )
  • the polymerizable unsaturated monomer (a2-1) having a urethane bond has a butyl urethane group.
  • Production and production example 8 of polymerizable unsaturated monomer (a3) having an imide bond In a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, air introduction tube, drying tube and dropping device, 52.4 parts of methacrylic acid, 47.6 parts of N-hydroxyethylphthalimide, 64.2 parts of toluene Then, 0.08 part of p-methoxyphenol and 4.7 parts of p-toluenesulfonic acid monohydrate were charged, and the temperature was raised to 130 ° C. while introducing dry air.
  • Production Examples 10 to 33 Synthesis was performed in the same manner as in Production Example 9 except that the composition shown in Table 1 below was used, to obtain macromonomer solutions (m-1-2) to (m-1-25) having a solid content of 65%.
  • Table 1 shows the raw material composition (parts) of the macromonomer solutions (m-1-1) to (m-1-25) and the polymerizable unsaturated monomers (a) and (b) in the monomer component (I). The ratio, hydroxyl value (mgKOH / g) and number average molecular weight are shown.
  • Examples 2 to 33, Comparative Examples 1 to 4 Synthesis was performed in the same manner as in Example 1 except that the formulation shown in Table 2 below was obtained, and copolymer dilutions (RC-2) to (RC-37) having a solid content of 20% were obtained.
  • Table 2 below shows the raw material composition (parts) and weight average molecular weight of the copolymer solutions (RC-1) to (RC-37).
  • NK-ester AM-90G trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polymerizable unsaturated monomer having a polyoxyalkylene chain, the following general formula (1) , R 1 is a hydrogen atom, R 2 is a methyl group, R 3 is an ethylene group, m is 9, and the molecular weight is 454.
  • Production and production example 34 of hydroxyl group-containing acrylic resin (A1) A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen gas inlet tube and dropping device, 128 parts deionized water, “ADEKA rear soap SR-1025” (trade name, manufactured by ADEKA, emulsifier, active ingredient) 25%) 3 parts were charged, stirred and mixed in a nitrogen stream, and heated to 80 ° C.
  • a water-dispersible hydroxyl group-containing acrylic resin aqueous dispersion (A1-1) having an average particle size of 95 nm and a solid content of 30% was obtained.
  • the obtained water-dispersible hydroxyl group-containing acrylic resin had an acid value of 33 mgKOH / g and a hydroxyl value of 22 mgKOH / g.
  • Monomer emulsion for core part 40 parts of deionized water, 2.8 parts of “ADEKA rear soap SR-1025”, 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 21 parts of n-butyl acrylate, 16 parts of methyl methacrylate .1 part and 28 parts of ethyl acrylate were mixed and stirred to obtain a monomer emulsion for the core part.
  • Monomer emulsion for shell part 17 parts of deionized water, 1.2 parts of “ADEKA rear soap SR-1025”, 0.03 part of ammonium persulfate, 3 parts of styrene, 9 parts of n-butyl acrylate, 2-hydroxyethyl methacrylate 5 .1 part, 5.1 parts of methacrylic acid, 6 parts of methyl methacrylate and 1.8 parts of ethyl acrylate were mixed and stirred to obtain a monomer emulsion for shell part.
  • Production Examples 35 to 38 A water-dispersible hydroxyl group-containing acrylic resin aqueous dispersions (A1-2) to (A1-5) were obtained in the same manner as in Production Example 34 except that the composition shown in Table 3 below was used.
  • Table 3 shows the raw material composition (parts), solid content (%), acid value (mgKOH / g) and hydroxyl value of water-dispersible hydroxyl group-containing acrylic resin aqueous dispersions (A1-1) to (A1-5) ( mgKOH / g).
  • Production Example 39 A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen gas inlet tube and dropping device was charged with 35 parts of propylene glycol monopropyl ether, heated to 85 ° C., then 30 parts of methyl methacrylate, 2-ethylhexyl acrylate 20 parts, 29 parts of n-butyl acrylate, 15 parts of 2-hydroxyethyl acrylate, 6 parts of acrylic acid, 15 parts of propylene glycol monopropyl ether and 2.3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) The mixture was added dropwise over 4 hours, and aged for 1 hour after completion of the addition.
  • hydroxyl group-containing acrylic resin solution (A1-6) having a solid content of 55%.
  • the obtained hydroxyl group-containing acrylic resin had an acid value of 47 mgKOH / g and a hydroxyl value of 72 mgKOH / g.
  • Production Example 40 A reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen gas inlet tube and dropping device, 128 parts deionized water, “ADEKA rear soap SR-1025” (trade name, manufactured by ADEKA, emulsifier, active ingredient) 25%) 3 parts were charged, stirred and mixed in a nitrogen stream, and heated to 80 ° C.
  • a hydroxyl group-containing water-dispersible acrylic resin aqueous dispersion (A1-7) having an average particle size of 148 nm and a solid content of 30% was obtained.
  • the obtained water-dispersible hydroxyl group-containing acrylic resin had an acid value of 14.3 mgKOH / g and a hydroxyl value of 9.4 mgKOH / g.
  • Monomer emulsion for core part 46.2 parts deionized water, 0.79 part "AQUALON KH-10", 0.32 part ammonium persulfate, 3.0 parts ethylene glycol dimethacrylate, 64 parts methyl methacrylate, n-butyl A monomer emulsion for core part was obtained by mixing and stirring 10 parts of acrylate.
  • Monomer emulsion for shell part 13.8 parts of deionized water, 0.24 part of “AQUALON KH-10”, 0.03 part of ammonium persulfate, 2.3 parts of methyl methacrylate, 6.44 parts of n-butyl acrylate, styrene 2.98 parts, 2.19 parts of 2-hydroxyethyl methacrylate, 2.19 parts of methacrylic acid, and 6.9 parts of the polymerizable unsaturated monomer (a1-1) having a urea bond obtained in Production Example 1 were mixed and stirred. By doing this, the monomer emulsion for shell parts was obtained.
  • Production Example 41 Same as Production Example 40 except that the polymerizable unsaturated monomer (a1-1) in the monomer emulsion for shell part is replaced with the polymerizable unsaturated monomer (a1-2) having a urea bond obtained in Production Example 2.
  • a hydroxyl group-containing water-dispersible acrylic resin aqueous dispersion (A1-8) having an average particle diameter of 142 nm and a solid content of 30% was obtained.
  • the obtained water-dispersible hydroxyl group-containing acrylic resin had an acid value of 14.3 mgKOH / g and a hydroxyl value of 9.4 mgKOH / g.
  • Production Example 42 The same procedure as in Production Example 40 except that the polymerizable unsaturated monomer (a1-1) in the monomer emulsion for shell was replaced with the polymerizable unsaturated monomer (a2) having a urethane bond obtained in Production Example 7.
  • the obtained water-dispersible hydroxyl group-containing acrylic resin had an acid value of 14.3 mgKOH / g and a hydroxyl value of 9.4 mgKOH / g.
  • Production Example 43 The same procedure as in Production Example 40 except that the polymerizable unsaturated monomer (a1-1) in the monomer emulsion for shell was replaced with the polymerizable unsaturated monomer (a3) having an imide bond obtained in Production Example 8.
  • the obtained water-dispersible hydroxyl group-containing acrylic resin had an acid value of 14.3 mgKOH / g and a hydroxyl value of 9.4 mgKOH / g.
  • the resulting condensation reaction product was added with 38.3 parts of trimellitic anhydride and reacted at 170 ° C. for 30 minutes, and then 2-ethyl-1-hexanol (20
  • the resulting solution was diluted with 0.1 g of a mass dissolved in 100 g of water at 0 ° C. to obtain a hydroxyl group-containing polyester resin solution (A2-1) having a solid content of 70%.
  • the obtained hydroxyl group-containing polyester resin had an acid value of 46 mgKOH / g, a hydroxyl value of 150 mgKOH / g, and a number average molecular weight of 1,400.
  • the total content of the alicyclic polybasic acid in the acid component was 46 mol% based on the total amount of the acid component.
  • a hydroxyl group-containing polyester resin solution (A2-2) having a solid content of 70% was obtained.
  • the obtained hydroxyl group-containing polyester resin had an acid value of 40 mgKOH / g, a hydroxyl value of 161 mgKOH / g, and a number average molecular weight of 1,300.
  • the total content of the alicyclic polybasic acid in the acid component was 28 mol% based on the total amount of the acid component.
  • Production Example 46 A hydroxyl group-containing polyester resin solution (A2) was prepared in the same manner as in Production Example 44, except that 2-ethyl-1-hexanol as a dilution solvent was changed to ethylene glycol monobutyl ether (mass dissolved in 100 g of water at 20 ° C .: infinite). -3) was obtained.
  • Production and production example 47 of aluminum pigment dispersion liquid In a stirring and mixing vessel, “GX-180A” (trade name, manufactured by Asahi Kasei Metals, aluminum pigment paste, aluminum content 74%) 19 parts (solid content 14 parts), 2-ethyl-1-hexanol 35 parts, 8 parts of phosphoric acid group-containing resin solution (4 parts of solid content) and 0.2 part of 2- (dimethylamino) ethanol were uniformly mixed to obtain an aluminum pigment dispersion (P-1).
  • GX-180A trade name, manufactured by Asahi Kasei Metals, aluminum pigment paste, aluminum content 74%) 19 parts (solid content 14 parts), 2-ethyl-1-hexanol 35 parts, 8 parts of phosphoric acid group-containing resin solution (4 parts of solid content) and 0.2 part of 2- (dimethylamino) ethanol were uniformly mixed to obtain an aluminum pigment dispersion (P-1).
  • Phosphate group-containing resin solution put a mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen gas inlet tube and dropping device.
  • the acid value due to the phosphoric acid group of this resin was 83 mgKOH / g, the hydroxyl value was 29 mgKOH / g, and the weight average molecular weight was 10,000.
  • Phosphoric acid group-containing polymerizable monomer put 57.5 parts of monobutyl phosphoric acid and 41 parts of isobutanol in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen gas introduction tube and dropping device, and bring After raising the temperature, 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours, followed by stirring and aging for another hour. Thereafter, 59 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid concentration of 50%. The acid value of the obtained monomer was 285 mgKOH / g.
  • Production Example 48 An aluminum pigment dispersion (P-2) was obtained in the same manner as in Production Example 47 except that 35 parts of 2-ethyl-1-hexanol was changed to 35 parts of ethylene glycol monobutyl ether.
  • Production Example 34 of water-based coating composition In a stirring and mixing container, 100 parts (30 parts solids) of the water-dispersible hydroxyl group-containing acrylic resin aqueous dispersion (A1-1) obtained in Production Example 34 and the hydroxyl group-containing acrylic resin solution (A1-6) obtained in Production Example 39 were used.
  • Examples 35 to 82 and Comparative Examples 5 to 10 Aqueous coating compositions (X-2) to (X-55) having a pH of 8.0 and a solid content of 25% were obtained in the same manner as in Example 34 except that the blending composition was as shown in Table 4 below. .
  • Fabrication production example 49 A 30 cm ⁇ 45 cm zinc phosphate-treated cold rolled steel sheet is coated with a thermosetting epoxy resin cationic electrodeposition coating composition (trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.) to a thickness of 20 ⁇ m. It was electrodeposited and cured by heating at 170 ° C. for 30 minutes. Next, an intermediate coating composition (trade name “TP-65-2”, manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type coating composition) is formed on the electrodeposition coating film so as to have a film thickness of 35 ⁇ m. And cured by heating at 140 ° C. for 30 minutes. Thus, an article to be coated formed by forming an electrodeposition coating film and an intermediate coating film on a steel plate was produced.
  • a thermosetting epoxy resin cationic electrodeposition coating composition trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.
  • an intermediate coating composition (trade name “TP-65-2”, manufactured by Kansai Paint
  • Coating film forming method Example 83 Using the aqueous coating composition (X-1) obtained in Example 34 as a base coat-forming coating in the two-coat one-bake method of the above-mentioned coating film forming method I, a base coat and a clear coat are applied on the article to be coated. A multilayer coating film was formed. That is, the aqueous coating composition (X-1) was applied to the article obtained in Production Example 49 to a film thickness of 15 ⁇ m using a rotary atomizing bell-type coater and left for 2 minutes. Thereafter, preheating was performed at 80 ° C. for 3 minutes.
  • an acrylic resin-based organic solvent-type clear clear coating composition (trade name “Magicron Kino-1210”, manufactured by Kansai Paint Co., Ltd.) was applied to the uncured coated surface so as to have a film thickness of 40 ⁇ m and left for 7 minutes. Thereafter, both coatings were cured simultaneously by heating at 140 ° C. for 30 minutes. Thus, a test plate was obtained in which a multilayer coating film composed of a base coat and a clear coat was formed on an object to be coated.
  • Examples 83 to 131 and Comparative Examples 11 to 16 Test plates of Examples 83 to 131 and Comparative Examples 11 to 16 were prepared in the same manner as Example 83, except that the aqueous coating composition shown in Table 5 was used instead of the aqueous coating composition (X-1). Got.
  • Example 132 A 30 cm ⁇ 45 cm zinc phosphate-treated cold rolled steel sheet is coated with a thermosetting epoxy resin cationic electrodeposition coating composition (trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.) to a thickness of 20 ⁇ m. It was electrodeposited and cured by heating at 170 ° C. for 30 minutes. Next, a first colored coating composition (trade name “TP-65-2”, manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type coating composition) is formed on the electrodeposition coating film to a thickness of 25 ⁇ m. After being coated for 5 minutes and then allowed to stand for 5 minutes, preheating was performed at 80 ° C. for 5 minutes.
  • a thermosetting epoxy resin cationic electrodeposition coating composition trade name “Electron GT-10” manufactured by Kansai Paint Co., Ltd.
  • TP-65-2 manufactured by Kansai Paint Co., Ltd., polyester resin / amino resin organic solvent type coating composition
  • the aqueous coating composition (X-1) was applied on the uncured coating surface to a film thickness of 15 ⁇ m using a rotary atomizing bell type coating machine for 2 minutes. After standing, preheating was performed at 80 ° C. for 3 minutes. Next, an acrylic resin-based organic solvent-type clear clear coating composition (trade name “Magicron Kino-1210”, manufactured by Kansai Paint Co., Ltd.) was applied to the uncured coated surface so as to have a film thickness of 40 ⁇ m and left for 7 minutes. Thereafter, this three-layer coating film was simultaneously cured by heating at 140 ° C. for 30 minutes.
  • the aqueous paint composition (X-1) obtained in Example 34 was used as a base coat-forming paint (second paint composition) in the 3-coat 1-bake method of the paint film-forming method II, and electrodeposition coating was performed.
  • a test plate was obtained in which a multilayer coating film comprising a first colored coating film, a second colored coating film, and a clear coat coating film was formed on the film.
  • Comparative Example 17 A test plate of Comparative Example 17 was obtained in the same manner as in Example 132 except that the aqueous coating composition (X-50) was used instead of the aqueous coating composition (X-1).
  • test plates obtained in Examples 83 to 132 and Comparative Examples 11 to 17 were evaluated for smoothness, sharpness, flip-flop properties, metallic unevenness, and water resistance.
  • the test method is as follows.
  • SW Short Wave
  • Flip-flop property Each test plate was visually observed at different angles, and the flip-flop property was evaluated according to the following criteria. S: The change in brightness depending on the viewing angle is remarkable (has extremely excellent flip-flop properties). A: The change of the brightness by a visual angle is large (excellent flip-flop property). B: The change in brightness depending on the viewing angle is slightly small (flip-flop property is slightly inferior). C: The change of the brightness by a visual angle is small (the flip-flop property is inferior).
  • Metallic unevenness Each test plate was visually observed, and the degree of occurrence of metallic unevenness was evaluated according to the following criteria. S: Metallic unevenness is hardly observed, and the coating film has an extremely excellent appearance. A: Although metallic unevenness is slightly observed, it has an excellent coating film appearance. B: Metallic unevenness is recognized and the coating film appearance is slightly inferior. C: Many metallic irregularities are observed, and the coating film appearance is poor.
  • Water resistance After immersing the test plate in warm water at 40 ° C. for 240 hours, pulling it up and drying at 20 ° C. for 12 hours, cut the multilayer coating film on the test plate into a lattice shape with a cutter so as to reach the substrate, Make 100 2mm x 2mm gobangs. Then, the adhesive cellophane tape was stuck on the surface, and the remaining state of the goby eye coating after the tape was rapidly peeled off at 20 ° C. was examined.
  • the evaluation criteria for water resistance are as follows. S: 100 Gobang eyes coating film remains and no flickering occurs, A: 100 pieces of gobang eye coat remain, but there are spots B: 90-99 gobanged paint films remain, C: The remaining number of gobang eye coats is 89 or less.

Abstract

La présente invention concerne un copolymère obtenu par copolymérisation d'un composant monomère (m) qui comprend à la fois (m-1) un macromonomère et (m-2) un monomère polymérisable ayant un groupe hydrophile. Le macromonomère (m-1) a à la fois un groupe insaturé polymérisable et un squelette basique consistant en une chaîne polymère qui est obtenue par polymérisation d'un composant monomère (I) consistant en 5 à 100 % en masse de (a) au moins un monomère polymérisable choisi dans le groupe consistant en (a1) les monomères insaturés polymérisables qui portent chacun une liaison urée, (a2) les monomères polymérisables qui portent chacun une liaison uréthane, et (a3) les monomères insaturés polymérisables qui portent chacun une liaison imide et 0 à 95 % en masse de (b) un monomère polymérisable autre que le monomère polymérisable (a) et qui a une masse moléculaire moyenne en nombre de 1 000 à 10 000.
PCT/JP2011/070229 2010-09-07 2011-09-06 Copolymère, composition de revêtement à base aqueuse le contenant et procédé de formation d'un film de revêtement multicouches WO2012033079A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010200275 2010-09-07
JP2010-200275 2010-09-07

Publications (1)

Publication Number Publication Date
WO2012033079A1 true WO2012033079A1 (fr) 2012-03-15

Family

ID=45810677

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/070229 WO2012033079A1 (fr) 2010-09-07 2011-09-06 Copolymère, composition de revêtement à base aqueuse le contenant et procédé de formation d'un film de revêtement multicouches

Country Status (1)

Country Link
WO (1) WO2012033079A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053204A (ja) * 2011-09-02 2013-03-21 Kansai Paint Co Ltd 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
WO2013140953A1 (fr) * 2012-03-23 2013-09-26 大日本塗料株式会社 Composition de peinture en résine époxy à base d'eau, procédé de peinture anticorrosive et corps peint
JP2013199621A (ja) * 2012-03-26 2013-10-03 Dainippon Toryo Co Ltd 水性エポキシ樹脂塗料組成物及びそれを用いた防食塗装方法
JP2019516813A (ja) * 2016-03-28 2019-06-20 ダウ グローバル テクノロジーズ エルエルシー 組成物、水性コーティング組成物、及び水性コーティング組成物の凍結／融解安定性を改善する方法
JP2019094437A (ja) * 2017-11-24 2019-06-20 日油株式会社 塗料用バインダー樹脂および塗料組成物
CN111635486A (zh) * 2020-05-08 2020-09-08 中山大桥化工集团有限公司 一种用于汽车闪光漆的水性丙烯酸乳液及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07508794A (ja) * 1992-10-30 1995-09-28 ピーピージー　インダストリーズ，インコーポレイテッド 耐酸エッチング性を有するカラー−クリアー複合コーティングを調製する方法
JPH0892455A (ja) * 1994-09-22 1996-04-09 Dainippon Ink & Chem Inc 水性ポリマーエマルジョン
JPH08231642A (ja) * 1994-12-29 1996-09-10 Basf Corp カルバメート官能性ポリマーの調製方法
JPH09221578A (ja) * 1995-08-10 1997-08-26 Basf Corp 耐環境腐食性コーティング用の水性コーティング組成物
JP2001031904A (ja) * 1999-05-28 2001-02-06 E I Du Pont De Nemours & Co 水不溶性の非イオングラフトコポリマーバインダー
JP2003503560A (ja) * 1999-06-28 2003-01-28 ビー・エイ・エス・エフ、コーポレーション カルバメート官能性ポリマーの製法
JP2003525324A (ja) * 2000-03-03 2003-08-26 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト 水性（メタ）アクリレートコポリマー分散液、その製造方法及びその使用
JP2007106871A (ja) * 2005-10-13 2007-04-26 Toray Fine Chemicals Co Ltd アクリル共重合体の製造方法および粘着剤組成物
JP2008150454A (ja) * 2006-12-15 2008-07-03 Kanae Toryo Kk 硬化型防曇コーティング剤組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07508794A (ja) * 1992-10-30 1995-09-28 ピーピージー　インダストリーズ，インコーポレイテッド 耐酸エッチング性を有するカラー−クリアー複合コーティングを調製する方法
JPH0892455A (ja) * 1994-09-22 1996-04-09 Dainippon Ink & Chem Inc 水性ポリマーエマルジョン
JPH08231642A (ja) * 1994-12-29 1996-09-10 Basf Corp カルバメート官能性ポリマーの調製方法
JPH09221578A (ja) * 1995-08-10 1997-08-26 Basf Corp 耐環境腐食性コーティング用の水性コーティング組成物
JP2001031904A (ja) * 1999-05-28 2001-02-06 E I Du Pont De Nemours & Co 水不溶性の非イオングラフトコポリマーバインダー
JP2003503560A (ja) * 1999-06-28 2003-01-28 ビー・エイ・エス・エフ、コーポレーション カルバメート官能性ポリマーの製法
JP2003525324A (ja) * 2000-03-03 2003-08-26 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト 水性（メタ）アクリレートコポリマー分散液、その製造方法及びその使用
JP2007106871A (ja) * 2005-10-13 2007-04-26 Toray Fine Chemicals Co Ltd アクリル共重合体の製造方法および粘着剤組成物
JP2008150454A (ja) * 2006-12-15 2008-07-03 Kanae Toryo Kk 硬化型防曇コーティング剤組成物

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053204A (ja) * 2011-09-02 2013-03-21 Kansai Paint Co Ltd 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
WO2013140953A1 (fr) * 2012-03-23 2013-09-26 大日本塗料株式会社 Composition de peinture en résine époxy à base d'eau, procédé de peinture anticorrosive et corps peint
CN104136559A (zh) * 2012-03-23 2014-11-05 大日本涂料株式会社 水性环氧树脂涂料组合物、防腐蚀涂装方法和涂装体
JP2013199621A (ja) * 2012-03-26 2013-10-03 Dainippon Toryo Co Ltd 水性エポキシ樹脂塗料組成物及びそれを用いた防食塗装方法
JP2019516813A (ja) * 2016-03-28 2019-06-20 ダウ グローバル テクノロジーズ エルエルシー 組成物、水性コーティング組成物、及び水性コーティング組成物の凍結／融解安定性を改善する方法
JP2019094437A (ja) * 2017-11-24 2019-06-20 日油株式会社 塗料用バインダー樹脂および塗料組成物
JP7034434B2 (ja) 2017-11-24 2022-03-14 日油株式会社 塗料用バインダー樹脂および塗料組成物
CN111635486A (zh) * 2020-05-08 2020-09-08 中山大桥化工集团有限公司 一种用于汽车闪光漆的水性丙烯酸乳液及其制备方法
CN111635486B (zh) * 2020-05-08 2023-01-13 中山大桥化工集团有限公司 一种用于汽车闪光漆的水性丙烯酸乳液及其制备方法

Similar Documents

Publication Publication Date Title
JP6180497B2 (ja) 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
JP5751614B2 (ja) 水性塗料組成物
JP5877829B2 (ja) 複層塗膜形成方法
JP6049747B2 (ja) 複層塗膜形成方法
JP5594931B2 (ja) 水性ベース塗料組成物
JP5653224B2 (ja) 複層塗膜形成方法
JP5759892B2 (ja) ベースコート塗料組成物
JP5116548B2 (ja) 顔料分散用樹脂の製造方法
JP5692890B2 (ja) 水性塗料組成物
JP5757662B2 (ja) 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
WO2012033079A1 (fr) Copolymère, composition de revêtement à base aqueuse le contenant et procédé de formation d'un film de revêtement multicouches
WO2016121241A1 (fr) Composition de revêtement aqueuse
JP5804661B2 (ja) 水性塗料組成物
JP5603177B2 (ja) 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
JP6076441B2 (ja) 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
JP5476260B2 (ja) 樹脂組成物、該樹脂組成物を含有する水性塗料組成物及び複層塗膜形成方法
JP5665132B2 (ja) 共重合体、該共重合体を含有する水性塗料組成物及び複層塗膜形成方法
WO2018079315A1 (fr) Polymère tribloc aba, agent d'ajustement de viscosité, et composition de revêtement aqueuse
WO2023089856A1 (fr) Composition de peinture
WO2023037688A1 (fr) Composition de revêtement
JP2023140372A (ja) アクリルウレタン複合樹脂、水性塗料組成物及び複層塗膜形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11823554

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11823554

Country of ref document: EP

Kind code of ref document: A1