JP5210506B2 - Water-dispersed slurry paint and coating film using the same - Google Patents

Description

  The present invention relates to a water-dispersed slurry paint and a coating film using the same, and more particularly to a water-dispersed slurry paint containing resin particles dispersed in an aqueous medium and a coating film using the same.

  Since the water-dispersed slurry paint has a form in which the resin particles are dispersed in water, it is necessary to suppress the coalescence and sedimentation of the resin particles over a long period of time and to stably disperse the resin particles in water.

From this point of view, surfactants are generally widely used (see, for example, Patent Document 1). For example, surfactants such as an anionic surfactant and a non-blocking surfactant having a hydrophobic portion at one end are known.
JP 2001-220544 A

  However, although the above anionic surfactants are excellent in storage stability, there is a problem of poor water resistance when a cured coating film is formed by coating and baking. In addition, when a non-blocking nonionic surfactant having a hydrophobic part at one end is used, there is a problem that the stability of the dispersed state at the time of storage is insufficient.

  As described above, the surfactants that have been widely used so far have not yet been able to impart a high degree of water resistance to the coating film when used as a paint while maintaining the storage stability after preparation of the paint. Currently.

  The present invention has been made in view of the above, and an object thereof is to provide a water-dispersed slurry paint excellent in water resistance when used as storage stability and a cured coating film, and a coating film excellent in water resistance. It is an object to achieve the object.

Specific means for achieving the object is as follows.
<1> Acrylic resin particles (A) in an aqueous medium [hereinafter also simply referred to as “resin particles (A)”. ] And a volume average particle diameter greater than the acrylic resin particles of the body volume average particle diameter of the acrylic resin particles (A) (B) [hereinafter simply referred to as "resin particle (B)". A] has a hydroxyl group and oxyethylene units in the hydrophilic portion, the first reactive surfactant average molecular weight of the urethane resin of 10,000 to 500,000 and (CL), the number-average molecular weight of 500 to 3000 urethane resin A water-dispersed slurry paint containing a second reactive surfactant (Cs).
<2> The mass ratio of the first reactive surfactant (CL) is based on the total mass of the first reactive surfactant (CL) and the second reactive surfactant (Cs). The water-dispersed slurry paint according to <1>, which is 20 to 95% by mass.

<3> The first reactive surfactant (CL) and / or the second reactive surfactant (Cs) contains an oxyethylene group as a hydrophilic group, and the total mass of the oxyethylene group is <1> or <2 characterized by being 20 to 97% by mass with respect to the total mass of the first reactive surfactant (CL) and the second reactive surfactant (Cs) > The water-dispersed slurry paint described in the above.
<4> The hydrophobic part of the first reactive surfactant (CL) and the second reactive surfactant (Cs) has a hydrocarbon group having 6 to 100 carbon atoms including an aromatic ring. The water-dispersed slurry paint according to any one of <1> to <3>, which is characterized.

<5 > The volume average particle diameter r ^{A of the} acrylic resin particles (A) is 0.03 to 0.2 μm, and the volume average particle diameter r ^{B of the} acrylic resin particles (B) is 0.3 to 10 μm. The ratio <r ^A / r ^B ) of the acrylic resin particles (A) and the acrylic resin particles ( ^B ) is 0.003 to 0.3, <1> to < 4 > The water-dispersed slurry paint according to any one of the above.
< 6 > A coating film using the water-dispersed slurry paint according to any one of <1> to < 5 >.

  ADVANTAGE OF THE INVENTION According to this invention, the water-dispersed slurry coating material excellent in water resistance when it is set as storage stability and a cured coating film, and the coating film excellent in water resistance can be provided.

  Hereinafter, the water-dispersed slurry paint of the present invention will be described in detail, and a coating film using the water-dispersed slurry paint will be described in detail.

  The water-dispersed slurry paint of the present invention comprises resin particles and a surfactant in an aqueous medium. Specifically, the water constituted in the first and second aspects shown below. Dispersed slurry paint. Moreover, it can comprise using other components, such as a hardening | curing agent, as needed.

  The aqueous medium refers to water or a mixed solvent of water-miscible solvent and water. Examples of the water-miscible solvent include alcohol solvents and ketone solvents. Specifically, alcohol solvents (for example, methanol, isopropanol, ethanol, n-propanol, etc.) and ketone solvents (for example, acetone, methyl ethyl ketone, etc.) can be mentioned. The mixing ratio of water to the water-miscible solvent in the mixed solvent is preferably 100/0 to 100/20, and more preferably 100/0 to 100/5.

-First embodiment-
A first aspect of the aqueous dispersion slurry coating of the present invention, at least, as the resin particles, acrylic resin acrylic resin particles containing (resin a) (A), includes an acrylic resin (resin b), the volume average particle diameter Urethane having a hydroxyl group and an oxyethylene unit in the hydrophilic part and having a number average molecular weight of 10,000 to 500,000 as a surfactant using acrylic resin particles (B) larger than the volume average particle diameter of the acrylic resin particles (A). first reactive surfactant is a resin (CL), in which the number-average molecular weight was constructed using the second reactive surfactant and (Cs) is a urethane resin 500-3000.

  In the first aspect, dispersibility is good by using a surfactant having a low number average molecular weight and a surfactant having a high number average molecular weight together with two kinds of organic particles having different volume average particle sizes in an aqueous medium. In addition to improving storage stability, it is also possible to improve water resistance when applied and baked to obtain a cured coating film.

< Acrylic resin particles (A)>
The water-dispersed slurry paint according to the first aspect contains at least one acrylic resin particle (A) containing an acrylic resin as the resin a. The resin particles (A) may be any of particles made of the resin a and particles containing other components such as a curing agent, a curing catalyst, and a pigment together with the resin a.

  The particle shape of the resin particles (A) may be indefinite or spherical, but spherical is preferred from the viewpoint of smoothness and uniformity of the coating film. Here, the spherical shape means that the ratio of the major axis / minor axis of the particles is in the range of 1.0 to 1.5.

The volume average particle diameter r ^A of the resin particles (A) is preferably 0.03 μm or more, more preferably 0.05 μm or more from the viewpoint of storage stability, and preferably from the viewpoint of coating film smoothness. It is 0.2 μm or less, more preferably 0.1 μm or less.
The volume average particle diameter r ^A can be measured by particle size distribution measurement by a dynamic light scattering method. Examples of the particle size distribution measuring device include DLS-7000 (manufactured by Otsuka Electronics Co., Ltd.). The measurement sample is measured, for example, by separating the dispersion or water-dispersed slurry paint with a centrifuge and diluting the supernatant with ion-exchanged water. Specifically, high-speed cooling centrifuge GRX-220 (manufactured by TOMY) rotor No. Centrifugation is performed for 5 minutes at 10000 rpm using 4II, and the supernatant is diluted 400-fold with ion exchange and measured.

The resin a can be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, a vinyl resin, Examples include polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Resin a may use 2 or more types of the said resin together.
Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.
The resin a preferably has a reactive functional group.

  Examples of the reactive functional group in the resin a include a carboxyl group, an epoxy group, a hydroxyl group, a hydrolyzable silyl group, a blocked carboxyl group, a blocked amino group, and a blocked isocyanate group, and storage during production and storage. From the viewpoint of stability, preferred are a carboxyl group, an epoxy group, a hydroxyl group, a blocked carboxyl group, a blocked amino group, and a blocked isocyanate group, and more preferred are an epoxy group, a hydroxyl group, and a blocked isocyanate group. .

  Examples of the blocking agent in the blocked carboxyl group include ammonia, tertiary alcohols (having 4 to 19 carbon atoms, for example, t-butanol, triethyl carbinol, tributyl carbinol, triphenyl carbinol) and vinyl compounds (having 4 to 4 carbon atoms). 18, for example, 2-methylpropene, 2-methylhexene) and the like. Among these, from the viewpoint of storage stability and ease of desorption during heat treatment, tertiary alcohols are preferable, and t-butanol and triethylcarbinol are more preferable.

  Examples of the blocking agent in the blocked amino group include ketones [having 3 to 15 carbon atoms, such as aliphatic ketones (acetone, methyl isobutyl ketone, etc.), aromatic ketones (benzophene, etc.), alicyclic ketones (dicyclohexyl ketone), etc. Can be mentioned. Of these, from the viewpoint of storage stability and ease of desorption during heat treatment, aliphatic ketones are preferred, and methyl isobutyl ketone is more preferred.

  Examples of the blocking agent in the blocked isocyanate group include oxime (3 to 10 carbon atoms such as acetoxime and methylethyl ethoxyme), alcohol (monohydric alcohol having 1 to 18 carbon atoms such as methyl alcohol, isopropyl alcohol, t- Butyl alcohol), phenol compounds [monohydric phenols having 6 to 20 carbon atoms, such as monocyclic phenols (phenol, nitrophenol, etc.), polycyclic phenols (1-naphthol, etc.)], lactams (4-15 carbon atoms, for example, γ-ptyrolactam, ε-caprolactam, γ-valerolactam) and the like. Of these, oxime and lactam are preferable from the viewpoint of storage stability and ease of desorption during heat treatment, and acetoxime and ε-caprolactam are more preferable.

  The number of reactive functional groups in the resin a1 molecule is preferably 1 or more, more preferably 2 or more, from the viewpoint of coating film strength. In addition, since the resin a may be a crosslinked resin, the upper limit cannot be described.

  As a method of forming the resin a by introducing the reactive functional group, a method of (co) polymerizing the monomer having the reactive functional group, a polymerization initiator having the reactive functional group (co) Examples include a method of performing polymerization, and a method of introducing a reactive functional group by modifying a resin after performing (co) polymerization. Among these, from the viewpoint of ease of introduction of the reactive functional group, a method of (co) polymerizing the monomer having the reactive functional group is preferable.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbon: (1-1) Aliphatic vinyl hydrocarbon: Alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-other than the above Olefin and the like; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

  (2) Carboxyl group-containing vinyl monomers and salts thereof: C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides and monoalkyl (C1-C24) esters thereof such as (meth) Acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoester, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid; and salts thereof.

  (3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropanesulfonic acid, 2- ( T) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-C18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, Propylene, butylene: single, random or block) Mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl-ter sulfate, and sulfuric acid Esters or sulfonic acid group-containing monomers; and salts thereof.

  (4) Phosphoric acid group-containing vinyl monomers and salts thereof: (Meth) acryloyloxyalkyl (C1-24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl Phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2-acryloyloxyethylphosphonic acid; and their salts.

  Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

  (5) Hydroxyl group-containing vinyl monomers: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth). Acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethyl Propenyl ether, sucrose allyl ether, etc.

  (6) Nitrogen-containing vinyl monomer: (6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole (6-2) Amido group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N -Methylene-bis (meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl Quaternization of tertiary amine group-containing vinyl monomers such as aminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and diallylamine (using quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate) Quaternized), (6-5) nitro group-containing vinyl monomer: nitrostyrene and the like.

  (7) Oxirane or oxolane group-containing vinyl monomers: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

  (8) Halogen element-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprune, and the like.

  (9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones: (9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diazyl adipate, isopropenyl Acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl having 1 to 50 carbon atoms (meth) Acrylate [Methyl (meth) acrylate, Ethyl (meth) acrylate, Propyl (meth) acrylate, Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups have 2 to 8 carbon atoms, straight chain, branched A chain or alicyclic group), a dialkyl maleate (two alkyl groups are straight-chain, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) aryl Roxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxyptan, tetrametaallyloxyethane, etc.] vinyl monomers having polyalkylene glycol chains [polyethylene Glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 5 00) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] etc .; (9-2) ) Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethylhexyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxy Styrene, phenoxystyrene, (9-3) vinyl ketone, such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl Sulfoxide etc.

  (10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-a, a-dimethylbenzyl isocyanate and the like.

Examples of the vinyl monomer copolymer include polymers obtained by copolymerizing any of the above monomers (1) to (10) in two or more and in any proportion. (Meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meta ) Acrylic acid copolymer, styrene- (meth) acrylic acid, divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.
The resin a is preferably nonionic. Here, the nonionic resin means a resin having no ionic functional group.

  Since it is necessary for the resin a to form the resin particles (A) in an aqueous medium, it is necessary that the resin a is not at least completely dissolved in the aqueous medium. Therefore, when the vinyl resin is a copolymer, the ratio between the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10% or more. It is preferable that it is 30% or more. When the ratio of the hydrophobic monomer is less than 10%, the vinyl resin becomes water-soluble, and the storage stability of the water-dispersed slurry paint of the present invention may be impaired. Here, the hydrophilic monomer means a monomer having a hydrophilic group, for example, a monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfone group, a phosphoric acid group, a thiol group or the like, and a salt thereof.

  Examples of the polyester resin include a polycondensate of a polyol and a polycarboxylic acid or its acid anhydride or its lower alkyl ester. The polyol is a diol (11) and a trivalent or higher polyol (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and a trivalent or higher polycarboxylic acid (14). And acid anhydrides or lower alkyl esters thereof. The ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3 / 1 to 1.02 / 1.

  Diol (11) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; Examples include polylactone diol (such as poly ε-caprolactone diol) and polybutadiene diol. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Examples of the trihydric or higher polyol (12) include 3 to 8 or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trisphenols (such as trisphenol PA) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins; acrylic polyol [copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Things. ] Etc. are mentioned. Of these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and alkylene oxide adducts of novolac resins, and particularly preferred are alkylene oxide adducts of novolac resins.

Dicarboxylic acid (13) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); carbon A branched alkylene dicarboxylic acid having a number of 8 or more [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.) ); Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). As the dicarboxylic acid (13) or the trivalent or higher polycarboxylic acid (14), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Examples of the method for introducing a reactive functional group (carboxyl group, hydroxyl group, etc.) into the polyester resin include a method for adjusting the equivalent ratio (COOH / OH) in the reaction between the carboxyl group-containing component and the hydroxyl group-containing component.
The appropriate ratio in the case of introducing a carboxyl group is preferably more than 1 and 10 or less, more preferably 1.1 to 3, and a hydroxyl group is introduced from the viewpoints of curability of the coating film and pigment dispersibility of the resin. The appropriate amount ratio in this case is preferably 0.2 or more and less than 1, more preferably 0.7 to 0.9, from the viewpoint of the weather resistance of the cured resin and the pigment dispersibility of the resin.
Examples of the method for producing the polyester resin include ordinary polyester polymerization methods such as a dehydration polycondensation reaction between a polycarboxylic acid and a polyol, and an ester exchange reaction between an ester-forming derivative of a polycarboxylic acid and a polyol.

  Examples of the polyurethane resin include polyisocyanate (15) and an active hydrogen group-containing compound {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid (13), and trivalent or higher polycarbonic acid ( 14), polyamines (16), polythiols (17) and the like} and the like.

As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 (except for carbon in NCO group) Alicyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurates Group, an oxazolidone group-containing modified product, and the like, and a mixture of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20 mass) %) Of tri- or higher functional polyamine]]: phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m− And p-isocyanatophenylsulfonyl isocyanate .

Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And aliphatic polyisocyanates.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included. Among these, preferred are 6-15 aromatic polyisocyanates, aliphatic polyisocyanates having 4-12 carbon atoms, and alicyclic polyisocyanates having 4-15 carbon atoms, and particularly preferred are TDI, MDI. , HDI, hydrogenated MDI and IPDI.

  Examples of polyamine (16) include aliphatic polyamines (C2 to C18): (1) Aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (2) these alkyls (C1-C4 ) Or a hydroxyalkyl (C2-C4) substituted product [dialkyl (C1-C3) aminopropynoramine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hex Methylenediamine, methyliminobispropylamine, etc.]; (3) Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; (4) Aromatic ring-containing aliphatic amines (C8-Cl5) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4-C15), 1,3- Heterocyclic polyamines (C4 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminonitrylpiperazine, 1,4- Aroma such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Polyamines (C6~C20);

(5) Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine) , Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylene diene Amines and the like; aromatic polyamines having nucleus substituted alkyl groups (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), such as 2,4- and 2,6-tolylenediamine, crude tri Range amine, diethyltolylenediamine, 4,4'-diamino- , 3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diamino Benzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5 -Diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5- Diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphtha 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5 ′ -Tetramethylbenzidine, 3,3 ', 5,5'-tetraisopropylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'- Tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,5-diisopropyl-3′-methyl-2 ′, 7,4-diaminodiphenyl Methane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diamino Benzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3, 3 ′, 5 5′-tetraisopropyl-4,4′-diaminodiphenyl sulfone, etc.), and mixtures of these isomers in various proportions;

(6) Aromatic polyamines [methylene bis-o-chloroaniline, 4-chloro-o] having nucleus-substituted electron withdrawing groups (halogens such as CI, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups) -Phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5- Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propa Bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) ) Selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoanidin), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2- fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; (7) aromatic polyamines [above having a secondary amino group (4) to (5) some or all of -NH ₂ of the aromatic polyamines Is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (methyl Mino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines (the above alkylenediamine, Polyalkylene polyamines and the like) and low molecular weight polyamide polyamines obtained by condensation with polyethers and polyamines: hydrides of cyanoethylated polyether polyols (polyalkylene glycols and the like).

  Examples of polythiol (17) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol and the like.

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (18), polyepoxide (18) and active hydrogen group-containing compound {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid (13 ) Or higher polyvalent polycarboxylic acids (14), polyamines (16), polythiols (17), etc.}, polyepoxides (18) and dicarboxylic acids (13) or trivalent or higher polycarboxylic acids ( 14) a cured product with an acid anhydride.

  The polyepoxide (18) in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). The epoxy equivalent of the polyepoxide (18) (molecular weight per epoxy group) is usually 65 to 1000, preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize one having an epoxy equivalent of less than 65. May be.

  Examples of the polyepoxide (18) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tert-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like.

Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like.
Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of p-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like.
The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidyl hexamethylenediamine.
In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

  The glass transition temperature (hereinafter referred to as Tg) of the resin a is preferably 0 ° C. to 100 ° C., more preferably 20 ° C. to 95 ° C., and more preferably 30 ° C. to 90 ° C. from the viewpoint of storage stability. . When Tg is lower than the temperature for producing the water-dispersed slurry paint, the effect of preventing coalescence is reduced. In addition, Tg in this invention is a value calculated | required from DSC measurement.

  From the viewpoint of reducing the dissolution or swelling of the resin particles (A) in water or a solvent used for dispersion, the molecular weight of the resin a, the SP value (the calculation method of the SP value is Polymer Engineering and Science, Feburary, 1974, Vol. 14, No. 2, P. 147 to 154), crystallinity, molecular weight between crosslinking points, and the like are preferably adjusted as appropriate.

  The number average molecular weight (measured by GPC; hereinafter abbreviated as Mn) of the resin a is usually 1000 or more, preferably 1400 or more, and the SP value is usually 7 to 18, preferably 8 to 14. Further, a crosslinked structure may be introduced into the resin a. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like.

  The content of the resin particles (A) in the water-dispersed slurry paint is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, based on the total weight of the paint. When the content of the resin particles (A) is within the above range, the storage stability is good and the water resistance is effectively improved.

< Acrylic resin particles (B)>
Aqueous dispersion slurry coating of the first aspect, the above with acrylic resin particles (A), includes an acrylic resin (resin b), the volume average particle diameter is larger than acrylic volume average particle diameter of the acrylic resin particles (A) Contains at least one resin particle (B).

  The resin particles (B) may be any of particles composed of the resin b and particles composed of the resin a and other components such as a coloring material such as a pigment and a dye, a curing agent, and a coating additive. . There is no restriction | limiting in particular about other components, such as a pigment and dye, A well-known thing can be selected suitably.

  The particle shape of the resin particles (B) may also be indefinite or spherical, but spherical is preferred in terms of the smoothness and uniformity of the coating film. As described above, the spherical shape means that the ratio of the major axis / minor axis of the particles is in the range of 1.0 to 1.5.

The volume average particle diameter r ^B of the resin particles (B) is preferably 0.3 μm or more, more preferably 1 μm or more, and even more preferably 1.2 μm or more, from the viewpoint of dryness in the baking step, and a smoothness viewpoint. Therefore, it is preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably 5 μm or less, and is selected to be larger than the volume average particle diameter of the resin particles (A) within this range.
The volume average particle diameter r ^B is measured using a flow type particle image analyzer, for example, FPIA-2100 manufactured by Sysmex Corporation, and the sample is obtained by diluting a water-dispersed slurry paint with ion-exchanged water, for example. it can.

From the viewpoint of storage stability, the volume average particle diameter [r ^A ] of the resin particles ( ^A ) and the volume average particle diameter [r ^B ] of the resin particles (B) are the particle size ratio {(resin particles (A) The volume average particle diameter r ^A ) / (volume average particle diameter r ^B ) of the resin particles ( ^B )} is preferably in the range of 0.003 to 0.3. When the particle size ratio is within the above range, the storage stability is good and the surface smoothness during coating is not impaired.
The value of the particle size ratio is more preferably 0.004 to 0.2, still more preferably 0.005 to 0.1.

  As the resin b constituting the resin particle (B), a preferable one can be appropriately selected according to the use, purpose, etc. Any resin can be used as long as it is a known resin as in the case of the resin a described above. Can be used. Specific examples thereof include those similar to the resin a. Specifically, polyurethane resins, epoxy resins, vinyl resins, and polyester resins are preferable. Moreover, it is preferable that the resin b has a reactive functional group like the resin a.

The number average molecular weight (Mn) of the resin b is usually 2,000 to 500,000, preferably 4,000 to 200,000.
The melting point of the resin b (measured by DSC; hereinafter, the melting point is a measured value by DSC) is usually 0 ° C. to 200 ° C., preferably 35 ° C. to 150 ° C. Moreover, Tg of resin b becomes like this. Preferably it is -50 degreeC-50 degreeC, More preferably, it is -40 degreeC-40 degreeC, More preferably, it is -37 degreeC-38 degreeC. The SP value of the resin b is usually 7 to 18, preferably 8 to 14.

  The content of the resin particles (B) in the water-dispersed slurry paint is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, based on the total weight of the paint. When the content of the resin particles (B) is within the above range, the storage stability is good and the coating property is effective.

  Among the above, a preferable combination of the resin particles (A) and the resin particles (B) is a combination in which (A) is a vinyl resin and (B) is an epoxy resin, and (A) is a vinyl resin. A combination in which (B) is a vinyl resin, (A) is polypropylene, (B) is a polyurethane, (A) is polyethylene, and (B) is a polyester resin. Some combinations, etc.

<Reactive surfactant>
The water-dispersed slurry paint according to the first aspect is one containing a surfactant together with the resin particles (A) and (B), and as the surfactant (reactive surfactant (C)), hydrophilic unit having a hydroxyl group and oxyethylene units, at least one and a number average molecular weight of 500 to 3000 urethane resin having a number average molecular weight of the first reactive surfactant is a urethane resin 10000 ~500000 (CL) And at least one second reactive surfactant (Cs).

The reactive surfactant (C) in the present invention comprises a hydrophobic part and a hydrophilic part, and at least the first reactive surfactant (CL) is one selected from a blocked isocyanate group, an epoxy group, an amino group and a hydroxyl group. Or , among two or more kinds of groups , it has a hydroxyl group in the hydrophilic part together with an oxyethylene unit , and the second reactive surfactant (Cs) is selected from a blocked isocyanate group, an epoxy group, an amino group, and a hydroxyl group It is preferable to have 1 type or 2 types or more of groups in a hydrophilic part.
As a hydrophobic part, what has a C6-C100 hydrocarbon group which has an aromatic ring is preferable. The hydrophilic portion, A anions groups in addition to the at least one group selected from the group consisting of cationic groups, and zwitterionic groups.

  Hereinafter, as the hydrophilic part, the reactive surfactant (C) having an oxyethylene unit is selected from the group of the reactive surfactant (C1) in the present invention, and the hydrophilic part is selected from the group of an anionic group, a cationic group, and a zwitterionic group. The reactive surfactant (C) having at least one group selected from the group consisting of the reactive surfactant (C2), an anionic group, a cationic group, and a zwitterionic group in the present invention. Let said reactive surfactant (C1) which has it be the reactive surfactant (C3) in this invention.

  The reactive surfactant (C) is one or two selected from a blocked isocyanate group, an epoxy group, an amino group, and a hydroxyl group from the viewpoint of water resistance of a film obtained from the aqueous dispersion obtained by using the reactive surfactant (C). The number of seeds is preferably 1 to 20, more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 5 per molecule of the reactive surfactant (C).

  The hydrophilic part of the reactive surfactant (C) has one or more hydrophilic groups of any one of an oxyethylene unit [polyoxyethylene group and the like], an anionic group, a cationic group, and a zwitterionic group. It is particularly preferable to have an oxyethylene unit.

When the hydrophilic group is particularly an oxyethylene unit, the oxyethylene unit is converted into the mass of the reactive surfactant (C) (that is, the first reactive surfactant (CL) and the second reactive surfactant ( Cs) is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 45% by mass or more, preferably 97% by mass or less, more preferably 90% by mass or less, Especially preferably, it is 80 mass% or less.
When the oxyethylene unit is 20% by mass or more and 97% by mass or less, the emulsifying power is strong and a stable slurry paint can be obtained.

The reactive surfactant (C) in the present invention has one or more hydrophobic parts. Examples of the hydrophobic part include hydrocarbon groups having 6 to 100 or more carbon atoms, preferably 8 to 80 carbon atoms and having an aromatic ring. Examples of the hydrocarbon group having an aromatic ring include a styrenated phenyl group, a residue excluding a hydroxyl group of bisphenols (such as bisphenol A, bisphenol S, and bisphenol F), and those obtained by adding a vinyl monomer to these compounds. Etc.
The hydrophobic part may also be a hydrophobic oxyalkylene unit other than an oxyethylene unit, such as an oxypropylene unit or an oxytetramethylene unit.

  The method for introducing the blocked isocyanate group and / or epoxy group is not particularly limited. For example, the isocyanate monomer (c2) which may be blocked and / or the vinyl monomer (c2 ′) having an epoxy group may be used. , A method of addition polymerization with other unsaturated monomers, a method of synthesizing a urethane resin composed of a polyoxyalkylene ether having a hydroxyl group or an amino group at the terminal, a diisocyanate and a blocking agent, a polyoxy having a hydroxyl group or an amino group at the terminal There is a method of reacting an alkylene ether and a diepoxy compound.

Specific examples of the isocyanate compound having a double bond include isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate butyl (meth) acrylate, isocyanate hexyl (meth) acrylate, 3-isopropenyl-α, α- Examples include dimethylbenzyl isocyanate, 3-ethylenyl-α, α-dimethylbenzyl isocyanate, and mixtures of two or more of the above.
Of these, preferred are 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 3-ethylenyl-α, α-dimethylbenzyl isocyanate.

Examples of the isocyanate group blocking agent include lactams (ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), phenols (phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, etc.), and oximes. (Methyl ethyl ketone oxime, acetophenone oxime, benzophenone oxime, etc.), alcohols (methanol, ethanol, butanol cyclohexanol, etc.), diketones (dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, ethyl acetylacetone, etc.), mercaptans (Butyl mercaptan, dodecyl mercaptan, etc.), uretdiones (isophorone diisocyanate dimer, hexamethylene diisocyanate dimer, etc.), Bromide compound (acetanilide, acetamide, etc.), imides (succinimide, maleimide, etc.) and sulfites (sodium bisulfite, etc.), and mixtures of two or more of the above.
Of these, alcohols, lactams, oximes, and phenols are preferable, and methanol, ethanol, and methyl ethyl ketone oxime are particularly preferable.

  The vinyl monomer (c2 ′) having an epoxy group is not particularly limited as long as it is various known compounds containing an epoxy group and a polymerizable vinyl group in the molecule. For example, unsaturated carboxylic acid glycidyl ester ((meta ) Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4 , 5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, methyl glycidyl (meth) acrylate), and unsaturated glycidyl ether (styrene- p-glycidyl ether, 2,3-diglycidyloxystyrene, 4-vinyl-1-cyclo Xene-1,2-epoxide, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 2,3-dihydroxymethyl Styrene diglycidyl ether, 3,4-dihydroxymethyl styrene diglycidyl ether, 2,4-dihydroxymethyl styrene diglycidyl ether, 3,5-dihydroxymethyl styrene diglycidyl ether, 2,6-dihydroxymethyl styrene diglycidyl ether, 2 , 3,4-Trihydroxymethylstyrene triglycidyl ether, 1,3,5-trihydroxymethylstyrene triglycidyl ether, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether Tellurium, vinyl phloroglicinol triglycidyl ether, etc.).

The other unsaturated monomer is not particularly limited, and aliphatic vinyl hydrocarbons, alicyclic vinyl hydrocarbons, and aromatic vinyl hydrocarbons can be used.
Examples of the aliphatic vinyl hydrocarbon include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1, 7-octadiene, α-olefins other than the above, and the like; examples of the alicyclic vinyl hydrocarbon include cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, ethylidenebicycloheptene, and the like; Examples of the group vinyl hydrocarbon include styrene, α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, Examples include tilbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, and trivinylbenzene.
A method for introducing a hydroxyl group or an amino group is not particularly limited, and examples thereof include a method of synthesizing a urethane resin composed of a polyoxyalkylene ether having a hydroxyl group or an amino group at a terminal and a diisocyanate.

  The reactive surfactant (C) of the present invention is preferably a urethane resin having at least one group selected from the group consisting of a blocked isocyanate group, an epoxy group, a hydroxyl group and an amino group. The urethane resin comprises an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (c1) and, if necessary, a vinyl monomer (c2) or an alkylene oxide adduct (c3) thereof, an organic diisocyanate (c4), a polyoxy The diol and / or diamine (c5) having an alkylene chain and the blocking agent (c6) or the polyepoxy compound (c7) are the main constituents, and an oxyethylene group is added to the (c3) and / or (c5). It is a urethane resin containing and added to (c3) and / or (c5) with at least one group selected from the group consisting of a blocked isocyanate group, an epoxy group, a hydroxyl group, and an amino group. The urethane resin may further use an extender (c8) as necessary.

  In the addition reaction with the monohydric phenol or monovalent aromatic alcohol (c1), the vinyl monomer (c2) and / or the vinyl monomer (c2 ′) having an epoxy group, and if necessary, an isocyanate group and You may use the vinyl monomer (c9) which does not have both an epoxy group.

The monohydric phenol is not particularly limited. For example, phenol, alkyl (having 1 to 18 carbon atoms) phenol (eg, nonylphenol, dodecylphenol, octylphenol), arylalkylated phenol (eg, cumylphenol), bisphenols And alkyl (carbon number 1 to 18) ethers (for example, monomethyl ether of bisphenol A, monobutyl ether of bisphenol A, monobutyl ether of bisphenol S, etc.) and mixtures of two or more of the above. Of these, preferred are phenol and cumylphenol.
Moreover, as monovalent | monohydric aromatic alcohol (c1), benzyl alcohol, 2-biphenylethanol, 4-biphenylethanol etc. are mentioned, for example. Of these, benzyl alcohol is preferred.

As said vinyl monomer (c2), the isocyanate compound which has the double bond mentioned above is mentioned.
Of these, preferred are 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 3-ethylenyl-α, α-dimethylbenzyl isocyanate.

The vinyl monomer having an epoxy group (c2 ′) is not particularly limited as long as it is a variety of known compounds containing an epoxy group and a polymerizable vinyl group in the molecule, and examples thereof include the above-described vinyl monomers having an epoxy group. Can do.
Of these, styrene-p-glycidyl ether and 2,3-diglycidyloxystyrene are preferred.

It does not specifically limit as a vinyl monomer (c9) which does not have both an isocyanate group and an epoxy group used as needed, The unsaturated monomer quoted above can be mentioned.
Of these, styrene is preferred.

In the addition reaction product or alkylene oxide addition product (c3) thereof, the monohydric phenol or monovalent aromatic alcohol (c1), the vinyl monomer (c2) and / or the vinyl monomer (c2 ′) having an epoxy group, The method for adding the vinyl monomer (c9) not having both the isocyanate group and the epoxy group as required is not particularly limited, but the Friedel-Crafts reaction is preferable.
As a method of Friedel-Crafts reaction, a known method can be used. For example, a monovalent phenol or a monovalent aromatic alcohol (c1) has a vinyl monomer (c2) having a blocked isocyanate group and / or an epoxy group. Examples include a method of polyadding the vinyl monomer (c2 ′) and, if necessary, the vinyl monomer (c9) using a known Lewis acid catalyst (for example, iron chloride, aluminum chloride, etc.).

In the present invention, the addition reaction product or its alkylene oxide adduct (c3) is also a vinyl having the monohydric phenol or monovalent aromatic alcohol (c1), the vinyl monomer (c2) and / or the epoxy group. An alkylene oxide may be further added to the addition reaction product obtained by adding the monomer (c2 ′) and, if necessary, the vinyl monomer (c9).
The alkylene oxide used (hereinafter abbreviated as AO, having 1 to 30 carbon atoms) is not particularly limited. For example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1, 2 -, 1,3- or 2,3-butylene oxide, tetrahydrofuran, α-olefin (4 to 30 carbon atoms) oxide, epichlorohydrin, styrene oxide, and a mixture of two or more of the above. Of these, EO is preferred. The addition mode is preferably random and / or block.
The number of moles of alkylene oxide added is preferably 1 to 30 moles, more preferably 1 to 10 moles, and still more preferably 1 to 5 moles.

  In the addition reaction product or the alkylene oxide adduct (c3), the monohydric phenol or monovalent aromatic alcohol (c1), the vinyl monomer (c2) and / or the vinyl monomer having the epoxy group as a structural unit. The weight ratio of (c2 ′), the vinyl monomer (c9) and the added AO is preferably (1-5) / (1-20) / (0-20) / (0-50), Preferably (1-3) / (1-10) / (1-10) / (1-25).

It does not specifically limit as organic diisocyanate (c4), For example,
(1) Aliphatic diisocyanate having 2 to 18 carbon atoms (excluding carbon in NCO group, the same shall apply hereinafter) [for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6- Diisocyanato hexanoate etc.];
(2) C4-C15 alicyclic diisocyanate [for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) Bis (2-isocyanatoethyl) -4-cyclohexene, etc.];
(3) C6-C14 aromatic diisocyanate [for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′ -Or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, etc.];
(4) C8-C15 araliphatic diisocyanate [for example, m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.];
(5) Modified products of these diisocyanates [eg, modified diisocyanates having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.];
(6) and a mixture of two or more of (1) to (5).
Of these, preferred are HDI, TDI and IPDI.

From the viewpoint of the emulsifying power of the reactive surfactant (C), the diol and / or diamine (c5) having a polyoxyalkylene chain is based on the mass of the diol and / or diamine (c5). Preferably it contains 20-100 mass%, More preferably, it is 50-100 mass%, Most preferably, it contains 70-100 mass%.
Examples of the diol and / or diamine (c5) include a polyether diol having a terminal hydroxyl group (c5-1), a polyester diol having a terminal hydroxyl group (c5-2), and a polyether diamine having a terminal amino group (c5-3). And the diol component alone, the diamine component alone, or both the diol component and the diamine component can be used.

  As the polyether diol (c5-1), for example, a low molecular diol, a compound having a structure in which AO is added to a dihydric phenol, a mixture of two or more of these, and the like can be used.

  The low molecular diol is not particularly limited, and examples thereof include ethylene glycol (hereinafter abbreviated as EG), diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (hereinafter abbreviated as 14BG), and 1,3-butanediol. , Neopentyl glycol, 1,6-hexanediol; low molecular diols having a cyclic group [for example, those described in JP-B No. 45-1474, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, bisphenol A And the like, and mixtures of two or more thereof.

  The dihydric phenol to which AO is to be added is not particularly limited, and for example, a dihydric phenol having 6 to 30 carbon atoms can be used. Specifically, monocyclic divalent, for example, catechol, resorcinol, hydroquinone and the like; condensed ring divalent, for example, dihydroxynaphthalene, etc .; bisphenol, for example, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl thioether, etc. And these alkyl (C1-C10) or halogen (chlorine, bromine, etc.) substitution products (for example, brominated bisphenol A) and the like.

  As the polyester diol (c5-2), for example, among the condensed polyester diols obtained by reacting the polyether diol (c5-1) having a number average molecular weight of 1000 or less with a dicarboxylic acid and / or a low molecular diol, Examples thereof include those containing polyoxyethylene units as described above.

Examples of the low molecular diol include those described above.
Examples of dicarboxylic acids include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, and sebacic acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, and phthalic acid), and ester forming properties of these dicarboxylic acids. Derivatives [acid anhydrides, lower alkyl (C1-4) esters, etc.] and mixtures of two or more of these may be mentioned.

As the polyether diamine (c5-3), one obtained by further converting the terminal hydroxyl group of the polyether diol (c5-1) to an amino group can be used.
As a method for converting the terminal hydroxyl group into an amino group, a known method can be used. For example, a terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of the polyether diol (c5-1) is reduced to an amino group. Examples include alkylating methods (for example, a method in which the polyether diol (c5-1) having a terminal hydroxyl group is reacted with acrylonitrile or nonenenitrile, and the resulting cyanoethylated product is hydrogenated).
Of these, preferred is a method in which the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of the polyether diol (c5-1) is reduced and aminoalkylated.

  The number average molecular weight per hydroxyl group and / or amino group of the diol and / or diamine (c5) is preferably 100 to 10,000 or more, more preferably 400 to 4,000.

  Examples of the extender (c10) used as necessary include water; low-molecular diols as described above; diamines [aliphatic diamines having 2 to 6 carbon atoms (for example, ethylenediamine, 1,2-propylenediamine, etc.) ), Alicyclic diamines having 6 to 15 carbon atoms (eg, isophorone diamine, 4,4′-diaminodicyclohexylmethane, etc.), aromatic diamines having 6 to 15 carbon atoms (eg, 4,4′-diaminodiphenylmethane, etc.)] Monoalkanolamine (such as monoethanolamine), hydrazine or a derivative thereof (such as adipic acid dihydrazide), and a mixture of two or more thereof. Of these, low molecular diols are preferable, and EG and 14BG are particularly preferable.

Moreover, it does not specifically limit as a terminator (c11), For example, a monohydric aliphatic alcohol (c11-1), an aliphatic monoamine (c11-2), etc. are mentioned.
Examples of the alcohol (c11-1) include C1-C18 saturated aliphatic monohydric alcohols (ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, 2-octyl alcohol, 2-ethylhexyl alcohol, etc. ), Unsaturated monohydric aliphatic alcohols having 1 to 18 carbon atoms (oleyl alcohol, etc.).

Examples of the monoamine (c11-2) include aliphatic monoamines having 1 to 18 carbon atoms [octylamine, 2-ethylhexylamine, dodecylamine, dibutylamine, dioctylamine, di (2-ethylhexyl) amine, etc.], carbon Examples thereof include unsaturated aliphatic monoamines having 1 to 18 carbon atoms (such as oleylamine) and monoamines having 1 to 16 carbon atoms (such as monoethanolamine and diethanolamine).
Among these, preferred are monohydric aliphatic alcohols and aliphatic monoamines, and particularly preferred are monohydric aliphatic alcohols.

  In the present invention, the urethane resin is preferably a compound represented by the following general formula (1).

[In the formula, Q is an adduct of a monohydric phenol or a monovalent aromatic alcohol (c1) and a vinyl monomer (c2) having a blocked isocyanate group and / or a vinyl monomer having an epoxy group (c2 ′) or its Residue of polyoxyalkylene ether (c3), G represents residue of organic diisocyanate (c4) optionally having urea bond, X represents O or NH, J represents polyoxyethylene unit The residue of the diol and / or diamine (c5) having a polyoxyalkylene chain to be contained, Z is hydrogen, a group represented by -COO-Q, or -CO-Y (Y is -OR ¹ ( R ^1: 1 monohydric residue of an alcohol) or ^-NR 1 to 18 carbon atoms ^{2 R} 3 ^(R 2: hydrocarbon group or a hydroxyalkyl group having 1 to 16 carbon atoms having 1 to 18 carbon atoms, ^3: hydrogen, hydroxy alkyl group)) or a hydrocarbon group having 1 to 16 carbon atoms having 1 to 18 carbon atoms, represents respectively. m is an integer of 1 to 500. ]

In the present invention, the method for producing the urethane resin is not particularly limited, and the adduct or its polyoxyalkylene ether (c3) to diol and / or the usual polyurethane resin production method (one-shot method or multistage method). It is obtained by subjecting the diamine (c5), if necessary, the extender (c10) and the terminator (c11) to a urethanization reaction. The reaction temperature of urethanization is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 8 hours.
The urethanization reaction is preferably carried out in a solventless system or in an organic solvent inert to isocyanates. Examples of the organic solvent include acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, toluene, dioxane and the like. The organic solvent is preferably removed by distillation or the like after producing a urethane resin.

In the urethanization reaction, the equivalent ratio [(OH + NH 2) / NCO ratio] of the hydroxyl (OH) group and amino group (NH ₂ ) to the isocyanate (NCO) group of the organic diisocyanate (c4) is preferably 1 :( 0.8 to 1.5), more preferably 1: (0.9 to 1.3). When the equivalent ratio of NCO groups is 0.8 to 1.5, the obtained polyurethane resin has an appropriate molecular weight, and the water resistance of the film from the obtained resin aqueous dispersion becomes good.

In the reactive surfactant (C2) of the present invention having an anion, a cation, or an amphoteric ion, the hydrophilic group is not particularly limited. For example, in the case of an anion group, a carboxylate group (—COO ⁻ X ⁺ ), Sulfonate group (—SO ³ −X ⁺ ), sulfate ester group (—OSO ³ —X ⁺ ), phosphate ester group (—OPO ₃ H ⁻ X ⁺ , —OPO ₃ ^{2 -} · 2X ⁺⁾ and the like (X, for example, sodium, potassium, ammonium, alkanolamine salts), group of primary amine salts if cationic group, group of salts of secondary amines, the third A group of a salt of a quaternary amine, a group of a quaternary ammonium salt or the like, and a zwitterionic group includes a hydrophilic group such as a betaine group.

  The content of the hydrophilic group is preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 5% by mass or more, preferably 50% by mass with respect to the mass of the reactive surfactant (C2). It is contained by mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less. When the content of the hydrophilic group is 0.1% by mass or more and 50% by mass or less, emulsifying power is strong and a stable slurry coating can be obtained.

  The reactive surfactant (C2) in the present invention is preferably a monovalent phenol or a monovalent aromatic alcohol (c1) and a vinyl monomer (c2) having a blocked isocyanate group and / or a vinyl having an epoxy group, for example. Residue of addition reaction product comprising monomer (c2 ′) or residue (c3 ′) of alkylene oxide adduct thereof and at least one ionic group selected from the group of anionic group, cationic group and zwitterionic group As the main component.

  At least one ionic group selected from the group of an anionic group, a cationic group, and a zwitterionic group may be added to any site in the residue (c3 ′). It can be added to a hydroxyl group introduced by phenol or a monovalent aromatic alcohol (c1), or a hydroxyl group introduced by adding an alkylene oxide to this hydroxyl group.

  In the present invention, the production method of the reactive surfactant (C2) is not particularly limited. For example, the above-mentioned adduct or the terminal hydroxyl group of the polyoxyalkylene ether (c3) is anionized (C2-1), It can be obtained by cationization (C2-2) or zwitterionization (C2-3).

  Examples of the anionization (C2-1) method include sulfate esterification of the above-mentioned adduct or the terminal hydroxyl group of the polyoxyalkylene ether (c3) with sulfuric anhydride, chlorosulfonic acid, etc., phosphoric anhydride, etc. And phosphoric acid esterification. The reaction temperature is preferably 20 ° C to 200 ° C, more preferably 20 ° C to 100 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 10 hours.

Examples of the method of cationization (C2-2) include neutralization of the aminated adduct or its polyoxyalkylene ether (c3) terminal with an acid and quaternization with an alkylating agent. It is done. The acid used for neutralization is not particularly limited, and examples thereof include hydrochloric acid and acetic acid. Examples of the alkylating agent used for quaternization include methyl chloride, methyl bromide, benzyl chloride, long chain alkyl chloride, epichlorohydrin, dimethyl sulfate, ethylene oxide, and the like. As a method for amination of the terminal, for example, acrylonitrile is added dropwise to the above-mentioned adduct or the hydroxyl group of the polyoxyalkylene ether (c3) in the presence of an alkali catalyst such as potassium hydroxide at 10 to 80 ° C. Thereafter, the alkali catalyst used is removed and hydrogenated using a catalyst such as nickel or cobalt in a solvent such as methanol under high pressure (for example, 30 to 100 kg / cm ² ).
The reaction temperature of the neutralization reaction is preferably 20 to 150 ° C, more preferably 20 to 100 ° C. The reaction time is preferably 0.1 to 20 hours, more preferably 0.1 to 6 hours.
The reaction temperature with the alkylating agent is preferably 50 to 300 ° C, more preferably 80 to 150 ° C. The reaction time is preferably 0.1 to 20 hours, more preferably 0.1 to 12 hours.

  Examples of the amphoteric ionization (C2-3) method include, for example, the terminal amino group of the adduct or its polyoxyalkylene ether (c3) is tertiaryized with the alkylating agent, and then an aqueous solution of sodium monochloroacetate. And a method in which a vinyl group-containing ester or vinyl group-containing nitrile is added and then saponified with an alkali. Examples of the vinyl group-containing ester include methyl acrylate and acrylonitrile.

  Further, the nonionic surfactant (C1) of the terminal OH is reacted to have at least one group selected from the group of anionic group, cationic group, and zwitterionic group. It becomes an activator (C3). The production can be carried out according to the above-mentioned production method of the reactive surfactant (C2).

  In the reactive surfactant (C3) in the present invention, the content of anionic group, cationic group, or zwitterionic group is preferably 0.1% by mass or more based on the mass of the reactive surfactant (C3). More preferably, it is 1% by mass or more, particularly preferably 5% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the content of the hydrophilic group is 0.1% by mass or more and 50% by mass or less, emulsifying power is strong and a stable slurry coating can be obtained.

In the first aspect of the water-dispersed slurry paint of the present invention, the hydrophilic part has a hydroxyl group and an oxyethylene unit , and a urethane resin reactive surfactant (CL) having a number average molecular weight of 10,000 to 500,000 and the number average. Use of a urethane resin reactive surfactant (Cs) having a molecular weight of 500 or more and 3000 or less is important for stable dispersion of fine particles and water resistance of the cured coating film after baking.
The number average molecular weight of the reactive surfactant (CL) is from 4,000 to 500,000, preferably from 10,000 to 70,000, more preferably from 13,000 to 50,000, and most preferably from 15,000 to 30,000 from the viewpoint of water resistance. is there. In the present invention, the reactive surfactant (CL) has a number average molecular weight of 10,000 to 500,000. The number average molecular weight of the reactive surfactant (Cs) is 500 or more and 3000 or less, preferably 800 or more, 2500 or less, particularly preferably 1000 or more and 2300 or less, and most preferably 1500 or more and 2000 or less, from the viewpoint of storage stability. It is.
Moreover, the combination in which both the reactive surfactant (CL) and the reactive surfactant (Cs) are nonionic surfactants is preferable.

The number average molecular weight is measured as a polystyrene equivalent value by gel permeation chromatography.
In order to adjust the number average molecular weight of the reactive surfactant, there are methods such as changing the molar ratio of monomers as raw materials, changing the temperature, time, and concentration during synthesis.

  In the present invention, the mass ratio of the reactive surfactant (CL) to the total mass of the reactive surfactant (CL) and the reactive surfactant (Cs) is 20% by mass to 95% by mass. It is preferable that it is 25 mass% or more and 80 mass% or less, and 30 mass% or more and 70 mass% or less are especially preferable.

The HLB of the reactive surfactant (C) is preferably 5 to 40 from the viewpoint of emulsifying the ethylenically unsaturated monomer and dispersing the resin fine particles to form a stable aqueous dispersion or aqueous emulsion. 5 to 20 is more preferable. The HLB of the reactive surfactant (C) is adjusted, for example, by adjusting the type and content of the hydrophobic group and the type and content of the hydrophilic group in the reactive surfactant (C). be able to. The HLB can be determined, for example, by the method of Oda described in Takehiko Fujimoto, “Full New Version, Introduction to Surfactant”, Sanyo Chemical Industries, Ltd., page 197. That is, the organic and inorganic numerical values obtained by evaluating the inorganic (hydrophilic) or organic (hydrophobic) numerical value of each functional group based on the number of carbon atoms (this numerical value is, for example, the third 3 and 11), the type of the hydrophobic group in the reactive surfactant (C) and its content, and the type and content of the hydrophilic group, An inorganic value is obtained, and HLB is calculated by the following formula.
HLB = 10 × (inorganic / organic)

  In the water-dispersed slurry paint according to the first aspect of the present invention, the content of the reactive surfactant (C) is based on the total mass of the resin particles (A) and (B) and the reactive surfactant (C). 0.1 to 10% by mass is preferable, more preferably 0.5 to 8% by mass, and most preferably 1 to 5% by mass.

-Second aspect-
The water-dispersed slurry paint of the second aspect of the present invention contains at least resin particles (A) containing resin a and resin b as resin particles, and the volume average particle diameter is the volume average of the resin particles (A). A resin particle (B) larger than the particle diameter, and as a surfactant, at least two hydrophobic portions (U) having a hydrocarbon group having 6 to 100 carbon atoms and having 1 to 12 aromatic rings, and oxy Using a surfactant (C1) having a repeating structure containing at least one hydrophilic part (W) having an ethylene chain as a repeating unit, both ends being terminal groups derived from the hydrophobic part (U) It is configured.

  In the second aspect, dispersibility is obtained by using a surfactant (C1) having both ends of the hydrophobic part (U) together with two kinds of organic particles having different volume average particle sizes in an aqueous medium. In addition, the storage stability can be improved, and the water resistance when coated and baked to obtain a cured coating film can also be improved.

  In addition, about the resin particle (A) and resin particle (B) in a 2nd aspect, it is the same as that of the resin particle (A) and resin particle (B) in the above-mentioned 1st aspect, A preferable aspect is also the same. is there.

<Surfactant (C1)>
The water-dispersed slurry paint according to the second aspect of the present invention comprises at least two hydrophobic units (U) having a hydrocarbon group having 6 to 100 carbon atoms containing 1 to 12 aromatic rings and an oxyethylene chain. It has at least one surfactant (C1) that has a repeating structure including at least one hydrophilic unit (W) as a repeating unit, and both ends are terminal groups derived from the hydrophobic portion (U).

  The hydrophobic part (U) is a repeating unit having a hydrocarbon group having 6 to 100 carbon atoms containing 1 to 12 aromatic rings, preferably a hydrocarbon group having 8 to 80 carbon atoms containing the aromatic ring. (The number of aromatic rings is preferably 2 to 10). When the carbon number is within the range, it is effective in terms of initial dispersibility of the resin b, and when the aromatic ring is within the range, it is effective in terms of storage stability.

  Examples of hydrocarbon groups having 1 to 12 aromatic rings include styrenated phenyl groups, residues other than hydroxyl groups of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), and vinyl monomers in these compounds. The one added is mentioned.

Hydrophobic section (U), the difference between the solubility parameter of the resin b in combination with the solubility parameter of the hydrophobic water portion (SP ^U) (SP ^b) is preferably is ^{0~3 (| | SP b -SP U} ) . If the difference in solubility parameter (SP value) is within the above range, it is effective in terms of the initial dispersibility of the resin b. Especially, it is preferably 0-2.

Here, the solubility parameter (SP value) is calculated by the Fedors method. The SP value can be expressed by the following equation.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ). ΔH and V are the total heat of molar evaporation (ΔH) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (151-153)”. And the sum of molar volumes (V) can be used.
This SP value is an index indicating that those having close values are easily mixed with each other (high compatibility), and those having a distant value are not easily mixed.

  The hydrophilic part (W) is a repeating unit having an oxyethylene chain (for example, a polyoxyethylene group), and the weight average molecular weight of the oxyethylene chain in one molecule of the surfactant (C1) is 1000 to 4000. More preferably, it is 1300-3500, More preferably, it is 1500-3000. When the oxyethylene chain is within the above range, a stable slurry paint can be obtained.

The repeating structure constituting the surfactant (C1) includes two or more hydrophobic parts (U) and one or more hydrophilic parts (W), and the hydrophobic part and the hydrophilic part are each located at the end. When this is done, a hydrogen atom is bonded to one of the two bonding hands and exists as a terminal group.
Accordingly, both ends of the surfactant (C1) are bonded with terminal groups derived from the hydrophobic part (U) in which a hydrogen atom is bonded to one of the two bonds of the hydrophobic part (U). The activator (C1) can further improve the water resistance after curing.

  The surfactant (C1) of the second embodiment has a repeating structure including two hydrophobic units (U) that are repeating units and one hydrophilic unit (W) that is a repeating unit. The minimum unit is “U-W-U”.

  In addition, the surfactant (C1) has a viewpoint of enhancing storage stability during production and storage, and water resistance after curing by bonding with other components such as resin particles and a curing agent that can be added as necessary. To a reactive surfactant having a reactive functional group, and preferably has at least one selected from a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, a blocked isocyanate group, and an epoxy group.

As a method of introducing a reactive functional group, a method of (co) polymerizing a monomer having a reactive functional group, a method of performing (co) polymerization using a polymerization initiator having a reactive functional group, (co) polymerization And a method of introducing a reactive functional group by modifying the surfactant.
Among these, the method of (co) polymerizing a monomer having a reactive functional group is preferable from the viewpoint of easy introduction of the reactive functional group.
The blocking agent in the blocked isocyanate group is the same as described above.

  Specific examples of the surfactant (C1) include, for example, surfactant C1-4 having a triblock structure of hydrophobic part-hydrophilic part-hydrophobic part obtained in Production Example 4 described later, and Production Example 5. And surfactant C1-5 having a multi-block structure of hydrophobic part-hydrophilic part-hydrophobic part-hydrophilic part-hydrophobic part.

  Among the surfactants (C1), a reactive surfactant having a triblock structure of hydrophobic part (U) -hydrophilic part (W) -hydrophobic part (U) is preferable.

The weight average molecular weight of the surfactant (C1) is preferably 1500 to 30000, more preferably 1800 to 28000, and still more preferably 2000 to 25000 from the viewpoint of storage stability.
The number average molecular weight is measured as a polystyrene equivalent value by gel permeation chromatography.

  In the water-dispersed slurry paint of the second aspect of the present invention, the content of the surfactant (C1) is 0. 0 relative to the total mass of the resin particles (A) and (B) and the surfactant (C1). 1-10 mass% is preferable, More preferably, it is 0.5-8 mass%, Most preferably, it is 1-5 mass%.

The resin content in the water-dispersed slurry paint of the present invention is preferably 20 to 75% by mass, and more preferably 20 to 60% by mass. Moreover, the viscosity at 25 ° C. is preferably 10 to 100,000 mPa · s, and more preferably 50 to 5,000 mPa · s.
When the resin content is 20 to 75 mass%, the dispersibility of the resin particles in water is good, and when the viscosity is 10 to 100,000 mPa · s, handling as a paint is easy.

  In addition, as long as the effect of the present invention is not impaired, the reactive surfactant (C) or the surfactant (C1) and, if necessary, other known emulsifiers or surfactants (nonionic emulsifiers and surfactants, anions) Emulsifiers and surfactants, cationic emulsifiers and surfactants, various reactive emulsifiers and surfactants) and the like can be used in combination. The amount of the other emulsifier and surfactant used in combination is preferably 44% by mass or less, more preferably 37% by mass or less, based on the total amount of the emulsifier or surfactant.

<Other ingredients>
In the water-dispersed slurry paint of the present invention, a known additive (C) (for example, a viscoelasticity adjusting agent, a reaction accelerator, a dynamic surface tension adjusting agent, a filler, a thickening agent, if necessary, depending on the intended use. Other components such as an agent, a heat or weather resistance stabilizer, a leveling agent, an antifoaming agent, a preservative, and a coloring agent) can be optionally contained.

  Examples of the viscoelasticity adjusting agent include, for example, polycarboxylic acid-based, polysulfonic acid-based, polyether-modified carboxylic acid-based, polyether-based polymer-type viscoelasticity adjusting agents, and urethane-modified polyether-based associative viscoelasticity adjusting agents. Agents. Moreover, reactive surfactant (C) or (C1) can also be used as a viscoelasticity adjusting agent. The blending amount is preferably 0.05% or more and 10.0% or less, more preferably 0.1 or more and 5% or less with respect to the slurry paint.

  Examples of the reaction accelerator include amine compounds such as diazabicyclooctane and 1,8-diazabicyclo (5,4,0) -undecene-7, and metal-containing compounds such as dibutyltin dilaurate and zirconium octylate. The blending amount is preferably 0.05% or more and 5.00% or less, more preferably 0.1% or more and 3% or less with respect to the slurry paint.

  Examples of the dynamic surface tension adjusting agent include acetylene glycol based dynamic surface tension adjusting agent, fluorine based dynamic surface tension adjusting agent, and silicone based dynamic surface tension adjusting agent. The blending amount is preferably 0.05% or more and 20.0% or less, more preferably 0.1 or more and 10% or less with respect to the slurry paint.

  Examples of the weathering stabilizer include salicylic acid ultraviolet absorbers such as phenyl salicylate and p-tert-butylphenyl salicylate, and benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, 2 Benzotriazole ultraviolet absorbers such as-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2-ethylhexyl-2-cyano Cyanoacrylate ultraviolet absorbers such as -3,3'-diphenyl acrylate, hindered amine light stabilizers such as octylated diphenylamine and isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate Raising It is. The blending amount is preferably 0.05% or more and 10% or less, more preferably 0.5% or more and 3% or less with respect to the slurry paint.

  Although it does not specifically limit as a leveling agent, For example, Olefin resins, such as low molecular polyethylene and low molecular polypropylene, Olefin copolymers, such as ethylene-acrylic copolymer and ethylene-methacrylic copolymer, (meth) acrylic copolymer And polyvinylpyrrolidone. The blending amount is preferably from 0.2% to 6%, more preferably from 0.5% to 3%, based on the slurry paint.

  Although it does not specifically limit as a coloring agent used as needed, For example, an inorganic pigment, an organic pigment, dye, etc. are mentioned. Examples of inorganic pigments include titanium oxide, carbon black, chromium oxide, and ferrite. Examples of the organic pigment include azo pigments such as azo lake, monoazo, disazo, and chelate azo, benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, Examples include an anthraquinone-based polycyclic pigment. Examples of the dye include nigrosine and aniline. The blending amount varies depending on the type of the colorant, but is preferably 0.5% or more and 30% or less, more preferably 1.0% or more and 10% or less with respect to the slurry paint.

Examples of the method for producing the water-dispersed slurry paint of the present invention include, but are not limited to, the following methods.
For example, a method of preferably mixing the resin particle (A) aqueous dispersion forming the lower layer and the resin particle (B) aqueous dispersion forming the upper layer is preferable. These are produced by the method exemplified below.
(1) Solvent removal method [In the aqueous medium containing the reactive surfactants (CL) and (Cs) or the surfactant (C1), the resin a or the resin b and, if necessary, the curing agent are dissolved in the organic solvent. Remove only the above water-miscible solvents and organic solvents so that the water remains by dispersing in a reaction vessel with a homomixer, etc., and reducing the pressure to 0.1-15 Torr while heating up to 100 ° C. if necessary. And dispersing fine particles in water];
(2) Grinding particle dispersion method [resin a or resin b, and if necessary, a curing agent is melt-kneaded, cooled and pulverized, and the resulting fine particles are converted into reactive surfactants (CL) and (Cs) or surface active Method of dispersing in reaction container with aqueous medium containing agent (C1) and disperser];
(3) Self-emulsification method [resin a or resin b containing a hydrophilic functional group such as a carboxyl group, and if necessary, a curing agent is dissolved in the organic solvent, and if necessary, a basic compound such as an amine compound is used. A method of dispersing fine particles obtained after or while neutralizing in water containing reactive surfactants (CL) and (Cs) or surfactant (C1)]

Among the above, the method (1) is preferable.
The concentration of the resin (a or b) in the production by the method (1) and, if necessary, the curing agent in the organic solvent is 20 to 75% by mass, preferably 40 to 60% by mass.
The concentration of the resin (a or b) obtained by the production method of the methods (1) and (2) and, if necessary, the curing agent in the dispersion is 5 to 70% by mass, preferably 30 to 60% by mass. is there.
The system temperature in the resin aqueous dispersion is usually -5 to 100 ° C, preferably 30 to 80 ° C, and the solvent removal is usually 0.1 to 50 hours, preferably 2 to 10 hours.

  Examples of the disperser used in the method for producing the aqueous resin dispersion include a homomixer, a disperser, a high-pressure homogenizer, a static mixer, a membrane emulsifier, a fill mix, and an ultrasonic disperser. Of these, a homomixer is preferable.

  The water-dispersed slurry paint of the present invention can be used as a top coat for automobiles or for coating various products such as buildings and home appliances.

  The water-dispersed slurry paint of the present invention can be applied using a spray coating machine, which is a conventional water paint paint equipment or solvent paint paint equipment, and does not require any new equipment. The coating film of the present invention is formed by using the water-dispersed slurry paint of the present invention described above. For example, the first or second water-dispersed slurry paint of the present invention is applied to a desired object to be coated. It is obtained by forming a film and baking the formed coating film.

  In the method of forming a coating film, the slurry paint is spray-coated on an object to be coated so that the wet film thickness is 10 μm or more and 200 μm or less, preferably 10 μm or more and 50 μm or less. Can be formed at a temperature of 120 ° C. to 180 ° C. by heating for 5 minutes to 60 minutes, preferably 5 minutes to 30 minutes, more preferably 5 minutes to 20 minutes. .

  The thickness of the coating film to be coated is preferably 10 μm or more and 150 μm or less, more preferably 15 μm or more and 50 μm or less.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

-Preparation of surfactant-
(Production Example 1)
In a reaction vessel equipped with a stirrer, dropping funnel, nitrogen gas inlet tube, thermometer, and reflux condenser, 53 parts of 4-α-cumylphenol and Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Co., Ltd.) 23 parts were charged, the inside of the system was replaced with nitrogen gas with stirring, and the temperature was raised to 90 ° C. At the same temperature, 181 parts of styrene was added dropwise over 3 hours, and further reacted at the same temperature for 5 hours. After cooling this to 30 ° C., the catalyst was filtered off to obtain 220 parts of 7 mol of styrene added to 1 mol of 4-α-cumylphenol (weight average molecular weight Mw: 900) (B0-1). It was.
EO (ethylene oxide) added to the obtained B0-1 [EO content 45 mass%, weight average molecular weight Mw: 1700] 16.9 parts, polyethylene glycol (weight average molecular weight Mw: 4000) 79.7 And 3.4 parts of hexamethylene diisocyanate (HDI) are reacted at 80 ° C. for 3 hours, and the polyoxyethylene chain has a weight average molecular weight Mw of 3600, an oxyethylene unit content of 87% by mass, a number average molecular weight of 24,000, hydrophobic As a result, 100 parts of a high molecular weight type reactive surfactant (CL-1) having a hydroxyl group and having 62 carbon atoms in the hydrocarbon group and HLB17.2 was obtained.

(Production Example 2)
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as the reactive surfactant (CL-1) of Production Example 1 [added 2 mol of styrene to 1 mol of 4-α-cumylphenol ] Is added EO (ethylene oxide), polyoxyethylene chain weight average molecular weight Mw 1100, oxyethylene unit content 87 mass%, weight average molecular weight Mw 1800, hydrophobic group hydrocarbon group carbon number 62, HLB13. 2, 100 parts of a low molecular weight type reactive surfactant (Cs-2) having a hydroxyl group was obtained.

(Production Example 3)
A polyoxyethylene chain was produced in the same manner as in Production Example 1 except that 3.4 parts of hexamethylene diisocyanate (HDI) in Production Example 1 was replaced with 3.7 parts of hydrogenated 4,4′-diphenylmethane diisocyanate (MDI). High molecular weight type reactive surfactant having a hydroxyl group having a weight average molecular weight Mw of 3600, an oxyethylene unit content of 87% by mass, a number average molecular weight of 24,000, a hydrocarbon group having 62 carbon atoms in the hydrophobic part, and an HLB of 17.2. 100 parts of an agent (CL-3) was obtained.

(Production Example 4)
B0-1 was obtained in the same manner as in Production Example 1, and EO (ethylene oxide) was added to the obtained B0-1 [EO content 45 mass%, weight average molecular weight Mw: 1700] 34.2 parts, polyethylene 80.2 parts of glycol (weight average molecular weight Mw: 4000) and 3.7 parts of hexamethylene diisocyanate (HDI) are reacted at 80 ° C. for 3 hours, and the weight average molecular weight Mw of polyoxyethylene chain is 3600 and the content of oxyethylene units. Surfactant (C1-4) 115 having 74% by mass, a number average molecular weight of 18,000, an aromatic ring number of 9 in the hydrophobic part, a carbon number of hydrocarbon group of 62, and an SP value of 11.2, having a hydrophobic part at both ends Got a part. The surfactant (C1-4) has a triblock structure of hydrophobic part-hydrophilic part-hydrophobic part.

(Production Example 5)
B0-1 was obtained in the same manner as in Production Example 1, and EO (ethylene oxide) was added to B0-1 obtained [EO content 45 mass%, weight average molecular weight Mw: 1700] 36.4 parts, BPE -20 (EO 2 mol adduct of bisphenol A, manufactured by Sanyo Chemical Industries, Ltd.) 10.2 parts, polyethylene glycol (weight average molecular weight Mw: 8000) 79.7 parts, and hexamethylene diisocyanate (HDI) 3.2 parts For 3 hours at 80 ° C., polyoxyethylene chain weight average molecular weight Mw 6400, oxyethylene unit content 76 mass%, number average molecular weight 28,000, hydrophobic part aromatic ring number 9, hydrocarbon group carbon number 62 parts of a surfactant (C1-5) having a hydrophobic part at both ends having an SP value of 11.2 were obtained. The surfactant (C1-5) has a multi-block structure of hydrophobic part-hydrophilic part-hydrophobic part-hydrophilic part-hydrophobic part.

-Preparation of particle dispersion-
A pressure-resistant reaction vessel was charged with ion-exchanged water, a surfactant, and ammonium persulfate as shown in Table 1 below. After the air in the reaction vessel was replaced with nitrogen, the reaction vessel was sealed, and stirring was started up to 80 ° C. The temperature rose. Subsequently, 200 parts of monomers mixed at the ratio (mass ratio) shown in Table 1 below were dropped over 2 hours. Further, the mixture was aged at the same temperature for 2 hours to obtain particle dispersions (AL-6, AL-7).

  With respect to the obtained particle dispersions AL-6 and 7, the volume average particle diameter of the resin particles in each dispersion was measured using a dynamic light scattering particle diameter measurement method (measurement using DLS-7000 manufactured by Otsuka Electronics Co., Ltd.). A sample prepared by diluting the particle dispersion AL-6,7 400 times with ion-exchanged water was used. The measurement results are shown in Table 1 below.

(Examples 1 to 3, Reference Examples 4 to 5, Comparative Examples 1 to 3)
-Preparation of water-dispersed slurry paint-
According to the blending ratio shown in Table 2 below, ion-exchanged water, the particle dispersion (AL-6, AL-7) obtained from the above, and the surfactants obtained in Production Examples 1 to 5 were blended and stirred well. did. Further, a mixed solution of resin b (SP value 9.1), curing agent, curing catalyst, and solvent (ethyl acetate) was added, and the resulting mixed solution was added to a TK homomixer (Special Machine Industries, Ltd. For 2 minutes. At this time, in Examples 1 and 3 , Reference Examples 4 to 5 and Comparative Examples 1 to 3, the rotation speed was 10,000 rpm, and in Example 2, it was 8000 rpm.
Then, it moved to the pressure | voltage resistant reaction container, and it desolvated under reduced pressure, heating up to 40 degreeC, and obtained the resin particle dispersion liquid. By adding a rheology control agent to the obtained resin particle dispersion and stirring well, water-dispersed slurry paint containing resin particles A and resin particles B [JL-1 to JL-5 (Examples 1-3, Reference) Examples 4 to 5) and HL-1 to HL-3 (Comparative Examples 1 to 3)] were prepared.

The resulting water-dispersed slurry paint had a solid content concentration of about 35%.
As the resin b, Desmophen A575X (hydroxyl group-containing acrylic polymer, manufactured by Sumitomo Bayer Urethane Co., Ltd.) is used, and as a curing agent, Duranate TPA-B80E (HDI isocyanurate type blocked product, manufactured by Asahi Kasei Kogyo Co., Ltd.), Dibutyltin laurate was used as a curing catalyst, and Acrysol RM-8W (urethane modified associative rheology control agent, manufactured by Rohm and Haas) was used as a rheology control agent.

−Preparation of painted plate−
An epoxy paint is applied to a 0.8 mm thick cold-rolled steel sheet treated with zinc phosphate so as to have a thickness of 20 μm. After heat-curing at 170 ° C. for 30 minutes, a black intermediate coating for automobiles has a thickness of 30 μm. In this way, the test plate was prepared by air spray coating and heat-curing at 140 ° C. for 30 minutes.

  On this test plate, the water-dispersed slurry paints [JL-1 to JL-5 and HL-1 to HL-3] obtained from the above are each made into a film thickness of 40 to 60 μm using a commercially available air spray gun. After coating in this manner and pre-baking at 80 ° C. for 10 minutes, it was further baked and dried at 150 ° C. for 20 minutes to prepare a coated plate.

(Measurement / Evaluation)
Measurement of the volume average particle diameter of the water-dispersed slurry paint obtained above, evaluation of storage stability, and water resistance of the coated plate were performed. The measurement results are shown in Table 3 below.

-1. Volume average particle diameter-
The volume average particle size ((A) value) of the resin particles A in the water-dispersed slurry paints [JL-1 to JL-5 and HL-1 to HL-3] is measured by a dynamic light scattering particle size measuring method (the measuring instrument is Using DLS-7000 manufactured by Otsuka Electronics Co., Ltd., each water-dispersed slurry paint was centrifuged at 10,000 rpm for 5 minutes with a high-speed cooling centrifuge GRX-220 (manufactured by TOMY) rotor No. 4II, and the supernatant was ion exchanged. The sample was prepared by diluting 400 times with water. Further, the volume average particle diameter ((B) value) of the resin particles B in the water-dispersed slurry paint [JL-1 to JL-5 and HL-1 to HL-3] is calculated using a flow type particle image analyzer FPIA (Sysmex Corporation). Manufactured and measured samples were measured by diluting each water-dispersed slurry paint 400 times with ion-exchanged water).

-2. Storage stability
20 g of water-dispersed slurry paint [JL-1 to JL-5 and HL-1 to HL-3] is put into a cylindrical glass container having a height of 20 cm and a diameter of 3 cm, and left in a constant temperature bath at 40 ° C. for 10 days. The state of blocking (fusing) between particles was visually evaluated according to the following criteria.
<Standard>
○: Uniformly dispersed.
X: The precipitate was not redispersed even when the container was shaken.

-3. Water resistance
The coating film was immersed in water at 40 ° C. for 10 days, and the coating film surface after water immersion was visually evaluated according to the following criteria.
<Standard>
○: No whitening was observed in the coating film.
X: Whitening is remarkably recognized in the coating film.

  As shown in Table 3, the water-dispersed slurry paint of the present invention had good storage stability because fine particles were stably dispersed, and was excellent in water resistance of the cured coating film after baking. In contrast, the comparative water-dispersed slurry paint could not satisfy both the storage stability and the water resistance of the cured coating film.

Claims (6)

In an aqueous medium, the acrylic resin particles (A), the volume average particle diameter greater than the acrylic resin particles of the body volume average particle diameter of the acrylic resin particles (A) (B), the hydroxyl group and oxyethylene units in the hydrophilic portion a first reactive surfactant average molecular weight of the urethane resin of 10,000 to 500,000 and (CL), the number-average molecular weight of the second reactive surfactant is a urethane resin 500 to 3000 (Cs And water-dispersed slurry paint.   The mass ratio of the first reactive surfactant (CL) is 20 with respect to the total mass of the first reactive surfactant (CL) and the second reactive surfactant (Cs). It is -95 mass%, The water-dispersed slurry coating material of Claim 1 characterized by the above-mentioned.   The first reactive surfactant (CL) and / or the second reactive surfactant (Cs) contains an oxyethylene group as a hydrophilic group, and the total mass of the oxyethylene group is the first reactive surfactant (CLs). The water dispersion according to claim 1 or 2, wherein the water dispersion is 20 to 97 mass% with respect to a total mass of the reactive surfactant (CL) and the second reactive surfactant (Cs). Slurry paint.   The hydrophobic portion of the first reactive surfactant (CL) and the second reactive surfactant (Cs) has a hydrocarbon group having 6 to 100 carbon atoms including an aromatic ring. The water-dispersed slurry paint according to any one of claims 1 to 3. The volume average particle diameter r ^{A of the} acrylic resin particles (A) is 0.03 to 0.2 μm, the volume average particle diameter r ^{B of the} acrylic resin particles (B) is 0.3 to 10 μm, and acrylic resin particles (a) and any one of acrylic ratio of the volume average particle diameter of the resin particles (B) according to claim 1-4 ^{where (r} a / r ^B) is characterized by a 0.003 to 0.3 The water-dispersed slurry paint according to item. A coating film using the water-dispersed slurry paint according to any one of claims 1 to 5 .