JP4199725B2 - Water dispersion slurry paint - Google Patents

Description

  The present invention relates to a slurry coating composition. More specifically, the present invention relates to a slurry coating composition that is excellent in the dispersibility of a resin dispersed in water and the strength of a cured coating film after baking. In addition, the particle size of the dispersion resin is larger than that of conventional emulsion paints, so the amount of emulsifier and dispersant used can be reduced, and the water resistance of the coating film is excellent, and the workability is also low because the viscosity is low. It relates to a good slurry coating composition.

  Since the slurry paint has a form in which fine particles are dispersed in water, when this is used, a surfactant is used to suppress coalescence and settling of the fine particles and to stably disperse the fine particles in water. (Patent Document 1).

JP 2001-220544 A

  However, when the slurry is actually used as a paint using a surfactant, the surfactant remaining after the aqueous medium is evaporated and dried deteriorates the water resistance of the coating film. Further, these surfactants exhibit a plasticizing effect and deteriorate the coating film strength. Accordingly, an object of the present invention is to provide a water-dispersed slurry paint that is improved in the above problems and is excellent in water resistance and coating strength.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is selected from the group consisting of fine particles (A) comprising an active hydrogen group-containing resin (a1) in an aqueous medium, and a hydrophilic part and a hydrophobic part, and comprising an isocyanate group, a blocked isocyanate group and an epoxy group. A water-dispersed slurry paint comprising a reactive surfactant (B) having at least one kind of group in the hydrophilic portion, and a coating film comprising the paint.

  The water-dispersed slurry coating of the present invention exhibits excellent coating strength, and is excellent in coating properties such as water resistance of the cured coating.

Hereinafter, the present invention will be described in detail.
The reactive surfactants (B) and (B0) in the present invention are composed of a hydrophilic part and a hydrophobic part. In (B), the hydrophilic part is composed of an isocyanate group, a blocked isocyanate group, and an epoxy group. It has at least one selected group, and (B0) has at least one group selected from the group consisting of an amino group, a hydroxyl group and a carboxyl group. As a hydrophobic part, what has a C6-C100 hydrocarbon group containing an aromatic ring is preferable. The hydrophilic portion preferably has an oxyethylene group.

  The slurry paint of the present invention has at least one group selected from the group consisting of an isocyanate group, a blocked isocyanate group, and an epoxy group in the hydrophilic part of the reactive surfactant as a constituent component in (B), Since (B0) contains at least one group selected from the group consisting of an amino group, a hydroxyl group and a carboxyl group, the compatibility with the resin (a1) containing an active hydrogen group is low (B) Or, since the hydrophilic part of (B0) is directly bonded to (a1), compatibility with the coating film is improved, excellent coating film strength is exhibited, and coating properties such as water resistance of the cured coating film are exhibited. Are better. In addition, the dispersion stability of the resin is excellent when the paint is stored.

The hydrophilic part of (B) and (B0) preferably contains an oxyethylene group. The content of the oxyethylene group is preferably at least 20% by weight, more preferably at least 25% by weight, particularly preferably at least 30% by weight, preferably 97% by weight, based on the weight of (B) or (B0), respectively. % Or less, more preferably 95% by weight or less, particularly preferably 93% by weight or less. When the oxyethylene group is 20% by weight or more and 97% by weight or less, emulsifying power is strong and a stable slurry paint can be obtained.
Each of (B) and (B0) preferably contains an oxyethylene group in an amount of 70% by weight or more, more preferably 75% by weight or more, particularly preferably 80% by weight or more based on the weight of the hydrophilic part, It is 99% by weight or less, more preferably 98% by weight or less, and particularly preferably 97% by weight or less. When the oxyethylene group is 70% by weight or more and 99% by weight or less, the emulsifying power is strong and a stable slurry paint can be obtained.

  The weight ratio (BL / BH) between the hydrophilic part (BH) and the hydrophobic part (BL) of (B) and (B0) is preferably 4.0 or less, 0.03 or more, more preferably 3.0 or less, 0 .05 or more, particularly preferably 2.3 or less and 0.07 or more.

The hydrophilic group-hydrophobic group balance (hereinafter referred to as HLB) of (B) and (B0) is a viewpoint that a stable aqueous dispersion or aqueous emulsion is obtained by dispersing fine particles with the power to emulsify the ethylenically unsaturated monomer. Therefore, 5 to 20 is preferable, and 7 to 20 is more preferable. The HLB of (B) or (B0) may be adjusted by adjusting the type of hydrophobic group and the content thereof in (B) or (B0), and adjusting the type of hydrophilic group and the content thereof, for example. it can. 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 value of the above document). 3 and 11), the organic value and inorganicity of the hydrophobic group in the above (B) or (B0) and the content thereof, and the hydrophilic group and the content thereof. The sex value is obtained, and the HLB is calculated by the following formula.
HLB = 10 × (inorganic / organic)

  The reactive surfactants (B) and (B0) in the present invention contain one or more hydrophobic parts (BL). Examples of the hydrophobic part include those containing a hydrocarbon group containing 6 to 100 or more carbon atoms, preferably 8 to 80 carbon atoms, and containing an aromatic ring from the viewpoint of dispersion stability. Examples of the hydrocarbon group containing an aromatic ring include a residue obtained by removing a hydroxyl group from phenols, a compound obtained by adding a vinyl monomer to these compounds (BL1), bisphenols (bisphenol A, bisphenol S, bisphenol F, etc. ) And a residue obtained by adding a vinyl monomer to these compounds (BL2), phenol novolac resin (hydroxyl valences 1 to 8), cresol novolac resin (hydroxyl valences 1 to 8) to hydroxyl groups And residues obtained by adding a vinyl monomer to these compounds (BL3), residues obtained by removing hydroxyl groups from aromatic alcohols (BL4), and the like.

  Specific examples include (BL1): phenyl group, alkyl (C1-18) phenyl group (eg, nonylphenol, dodecylphenol, octylphenol, etc.), styrenated (addition mole number 1-10) phenyl group, arylalkylated phenol. (Eg, cumylphenol), styrenation (addition mole number 1-10) cumenyl (isopropylphenyl) group, etc. (BL2): bisphenyl group (bisphenol A, bisphenol S, bisphenol F, etc.), styrenation (addition mole number) 1-10) Bisphenyl group and the like (BL3): a residue obtained by removing a hydroxyl group from a phenol novolak resin (hydroxyl valence 1-8), styrenated (addition mole number 1-10) phenol novolac resin (hydroxyl valence) 1 to 8), a residue obtained by removing a hydroxyl group, a cresol novolak resin ( Residues obtained by removing hydroxyl groups from valences 1 to 8) of acid groups, residues obtained by removing hydroxyl groups from styrenated (addition moles 1 to 10) cresol novolak resins (valences 1 to 8 of hydroxyl groups), etc. (BL4) : Residue obtained by removing a hydroxyl group from benzyl alcohol. Among these, a styrenated (addition mole number 1-10) phenyl group and a styrenation (addition mole number 1-10) cumenyl group are preferable.

The reactive surfactants (B) and (B0) in the present invention contain one or more hydrophilic parts (BH).
Examples of the hydrophilic portion (BH) include the following groups (BH1) and (BH2) bonded to the phenolic or alcoholic hydroxyl group of the hydrophobic portion (BL). (BH1): In (B), a group obtained by removing one hydrogen from a polyoxyalkylene ether terminated with an isocyanate group, a blocked isocyanate group or an epoxy group, and (BH2): In (B), an isocyanate group In the group (B0), at least one group selected from the group consisting of a blocked isocyanate group and an epoxy group is terminated, and one hydrogen is removed from a urethane resin consisting of a polyoxyalkylene ether and a diisocyanate; A group obtained by removing one hydrogen from a urethane resin having at least one group selected from the group consisting of an amino group, a hydroxyl group and a carboxyl group at the end, and comprising a polyoxyalkylene ether and a diisocyanate.

  The method for introducing an isocyanate group or a blocked isocyanate group contained in the hydrophilic part of (B) is not particularly limited. For example, one end of an organic polyisocyanate is reacted with active hydrogen in the hydrophilic part, and the remaining NCO is left as necessary. There is a method of blocking the group.

The organic polyisocyanate is not particularly limited. 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) C8-15 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 these (1) to (5);
(7) Modified organic diisocyanate exemplified above (urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group or oxazolidone group-containing modified product), HDI isocyanurate, HDI burette, IPDI Isocyanurate, IPDI burette, crude MDI [crude diaminodiphenylmethane {condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] Phosgenates: polyallyl polyisocyanate (PAPI), etc.], and these blocked isocyanate compounds.
Of these, preferred are HDI, TDI and IPDI.

As isocyanate group blocking agents, lactams (ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), phenols (phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, etc.), oximes (methyl ethyl ketone) Oximes, acetophenone oximes, benzophenone oximes, etc.), alcohols (methanol, ethanol, butanol, cyclohexanol, etc.), diketones (dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.), mercaptans ( Butyl mercaptan, dodecyl mercaptan, etc.), uretdiones (isophorone diisocyanate dimer, hexamethylene diisocyanate dimer, etc.), amide (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 method for introducing an epoxy group contained in the hydrophilic portion of (B) is not particularly limited, and examples thereof include a method for introducing one end of a polyepoxy compound with active hydrogen in the hydrophilic portion to introduce an epoxy group. .

The polyepoxy compound is not particularly limited, for example,
Glycidyl ester of aromatic polycarboxylic acid (phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, trimellitic acid diglycidyl ester, etc.); glycidyl ether of polyhydric phenol (bisphenol F diglycidyl ether, Bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, Hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxy Obtained from the reaction of phthaline diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, polyglycidyl ether of phenol or cresol novolac resin, 2 mol of bisphenol A and 3 mol of epichlorohydrin Diglycidyl ether, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol and glycoxal, glutaraldehyde, or formaldehyde, and polyglycidyl ether of polyphenol obtained by condensation reaction of resorcin and acetone); glycidyl aromatic Polyamines (N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine, etc.); alicyclic Riepoxy compounds (vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, etc.) Can be mentioned. Preferred are bisphenol F diglycidyl ether and bisphenol A diglycidyl ether.

  The method for introducing a hydroxyl group, amino group or carboxyl group contained in the hydrophilic part of (B0) is not particularly limited. For example, a urethane resin composed of a polyoxyalkylene ether having a hydroxyl group or amino group at one end and a diisocyanate is synthesized. And a method of introducing a carboxyl group as necessary.

  The reactive surfactant (B) of the present invention is preferably a urethane resin (B1) having at least one group selected from the group consisting of an isocyanate group, a blocked isocyanate group, and an epoxy group. The urethane resin (B1) is an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (b1) and, if necessary, a vinyl monomer (b2), or an alkylene oxide adduct (b3) thereof, an organic diisocyanate (b4). A diol and / or a diamine (b5) having a polyoxyalkylene chain, and a blocking agent (b6) or a polyepoxy compound (b7) as main components, and (b3) and / or (b5) A urethane resin containing an ethylene group and having (b3) and / or (b5) added 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. (B1) may further use an extender (b8) as necessary.

  Polyoxyethylene chains in the reactive surfactants (B) and (B0) [above (b3) and (b5), or the following (b3 ′), or the following (b3 ″) and (b5 ′) The weight average molecular weight (hereinafter abbreviated as MW) of the ethylene chain is preferably 1,000 to 4,000, more preferably 1,500 to 3,800, particularly preferably 2,000 to 4,000 from the viewpoint of water resistance. 3,500.

  The MW of the polyoxyethylene chain in the above (B) and (B0) can be calculated by calculating the MW of each polyoxyethylene chain by the hydroxyl value or GPC and calculating the weighted arithmetic average with respect to the weight used.

  Urethane resin (B1) consists of 1 type, or 2 or more types of the compound represented by the following general formula (1) or (2), for example.

Q-(-CONH-G-NHCO-J-) _m -CONH-G-NHCO-Y (1)
Q-(-CONH-G-NHCO-J-) _m -Z (2)

  In the formula, Q is a residue of an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (b1) and, if necessary, a vinyl monomer (b2) or an alkylene oxide adduct (b3) thereof, and G is an organic The residue of the diisocyanate (b4), J is the residue of the diol and / or diamine (b5) having a polyoxyalkylene chain, Y is the residue of the blocking agent (b6), Z is the polyepoxy compound ( represents the residue of b7). A plurality of G and a plurality of J may be the same or different. m is preferably 1-20, more preferably 1-10.

The weight average molecular weight (hereinafter abbreviated as MW) of (B1) is preferably 1,000 to 150,000, more preferably 1,500 to 30,000, more preferably 2,000 to 20,000, and particularly preferably. Is 3,000 to 15,000. MW is preferably 1,000 or more, more preferably 1,500 or more, in terms of obtaining sufficient surface active ability, and preferably 150,000 or less in terms of obtaining a stable aqueous resin dispersion with low viscosity. 30,000 or less is more preferable. In addition, MW can be measured by a gel permeation chromatography (GPC) method.

The (b1) constituting the (B) is not particularly limited, and examples thereof include phenol, alkyl (C 1-18) phenol (eg, nonylphenol, dodecylphenol, octylphenol, etc.), arylalkylated phenol (eg, cumylphenol). Etc.), monoalkyl (carbon number 1 to 18) ethers of bisphenols (eg, monomethyl ether of bisphenol A, monobutyl ether of bisphenol A, monobutyl ether of bisphenol S, etc.), aromatic alcohols (eg, benzyl alcohol, etc.) and the above Or a mixture of two or more thereof.
Of these, preferred are phenol and cumylphenol.

Examples of the vinyl monomer (b2) include vinyl monomers having no isocyanate group. For example, 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, Examples of alicyclic vinyl hydrocarbons such as 7-octadiene, α-olefins other than the above 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.
Of these, styrene is preferred.

The (b3) is an addition reaction product composed of the monohydric phenol or monovalent aromatic alcohol (b1) and, if necessary, the vinyl monomer (b2) or an alkylene oxide adduct thereof.
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 (having 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 added mole number of alkylene oxide is 1 to 30 mol, preferably 1 to 10 mol, more preferably 1 to 5 mol.

  The MW of (b3) is preferably 300 to 20,000, more preferably 400 to 15,000, more preferably 500 to 10,000, particularly preferably 1,000 to 4,000, very preferably 1,500 to 3,800, most preferably 2,000-3,500. The MW is preferably 300 or more, more preferably 1,000 or more in terms of obtaining sufficient surface active ability, and preferably 20,000 or less in terms of obtaining a stable aqueous resin dispersion having a low viscosity. In view of the above, 4000 or less is more preferable.

  In the above (b3), the weight ratio of the structural units (b1), (b2) and added AO is preferably (1-5) / (0-99) / (0-99), Preferably (1-5) / (1-60) / (1-60).

  Specific examples of (b3) include, for example, styrenated (1 to 10 mol addition) phenol EO addition (1 to 25 mol), styrenated (1 to 10 mol addition) cumylphenol EO addition (1 to 25 mol) ) Product.

In (b3) above, the method of adding (b1) and (b2) above is not particularly limited, but is preferably based on the Friedel-Crafts reaction.
As a Friedel-Crafts reaction method, a known method can be used. For example, a vinyl monomer (b2) is optionally added to a monovalent phenol or a monovalent aromatic alcohol (b1) and a known Lewis acid catalyst ( Examples thereof include a method of polyaddition using iron chloride, aluminum chloride, etc.).

  It does not specifically limit as organic diisocyanate (b4), For example, what is illustrated above is mentioned.

The diol and / or diamine (b5) having a polyoxyalkylene chain is preferably 20 to 100% by weight, more preferably the polyoxyethylene unit based on the weight of (b5), from the viewpoint of the emulsifying power of (B). Contains 50 to 100% by weight, particularly preferably 70 to 100% by weight.
Examples of (b5) include a polyether diol having a terminal hydroxyl group (b5-1), a polyester diol having a terminal hydroxyl group (b5-2), and a polyether diamine having a terminal amino group (b5-3). Only the component, only the diamine component, or both the diol component and the diamine component can be used.

  As the above (b5-1), for example, a low molecular diol or 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. For example, ethylene glycol (hereinafter abbreviated as EG), diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (hereinafter abbreviated as 14BG), 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.

  It does not specifically limit as said dihydric phenol, For example, C6-C30 bivalent phenol 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, dihydroxy diphenyl ether, dihydroxy diphenyl thioether, etc .; And binaphthol; and alkyl (1 to 10 carbon atoms) or halogen (chlorine, bromine, etc.) substitutes thereof (for example, brominated bisphenol A).

  Examples of (b5-2) include polyoxyethylene units as described above in a condensed polyester diol obtained by reacting (b5-1) having a MW of 1000 or less with a dicarboxylic acid and / or a low molecular diol. The thing etc. which are contained are mentioned.

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 said (b5-3), what is obtained by further changing the terminal hydroxyl group of said (b5-1) into 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, the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group in the above (b5-1) is reduced and aminoalkylated. Examples thereof include a method (for example, a method of reacting (b5-1) having a terminal hydroxyl group with acrylonitrile or nonenenitrile and hydrogenating the resulting cyanoethylated product).
Of these, preferred is a method in which the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of (b5-1) is reduced and aminoalkylated.

  The MW of (b5) is usually preferably from 200 to 10,000 or more, more preferably from 600 to 6,000. More preferably, it is 1,000-4,000, Most preferably, it is 1,500-3,800, Most preferably, it is 2,000-3,500. The MW is preferably 200 or more from the viewpoint of obtaining sufficient surface active ability, and preferably 10,000 or less from the viewpoint of water resistance.

  As said (b6), what was mentioned as a blocking agent of the said isocyanate group can be used.

  As the polyepoxy compound (b7), those mentioned as the polyepoxy compound can be used.

  As a component of the reactive surfactant (B1), an extender (b8) may be included as necessary. As (b8), water; low molecular diol described above; diamine [aliphatic diamine having 2 to 6 carbon atoms (for example, ethylenediamine, 1,2-propylenediamine, etc.), alicyclic having 6 to 15 carbon atoms Diamine (eg, isophorone diamine, 4,4′-diaminodicyclohexylmethane, etc.), C6-C15 aromatic diamine (eg, 4,4′-diaminodiphenylmethane, etc.), etc .; Monoalkanolamine (eg, monoethanolamine, etc.) Hydrazine or a derivative thereof (for example, 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.

The reactive surfactant (B) of the present invention also includes an alkylene oxide adduct (b3 ′) which is an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (b1) and, if necessary, a vinyl monomer (b2). ), And a blocking agent (b6) or a polyepoxy compound (b7) as main constituents, (b3 ′) contains an oxyethylene group, (b3 ′) contains an isocyanate group, a blocked isocyanate group and an epoxy. A compound (B2) obtained by adding at least one group selected from the group consisting of groups is preferable.
The alkylene oxide in (b1), (b2), (b6), (b7), (b3 ′) is the same as that in (B1).

The reactive surfactant (B2) comprises, for example, one or more compounds represented by the following general formula (3) or (4).
Q'-CONH-G-NHCO-Y (3)
Q'-Z (4)
In the formula, Q ′ is a residue of an alkylene oxide adduct (b3 ′) of an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (b1) and, if necessary, a vinyl monomer (b2), and G is , Y represents the residue of the organic diisocyanate (b4), Y represents the residue of the blocking agent (b6), and Z represents the residue of the polyepoxy compound (b7).

The MW of (B2) is preferably 1,500 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000. The MW is preferably 1,500 or more from the viewpoint of obtaining sufficient surface active ability, and preferably 30,000 or less from the viewpoint of obtaining a stable aqueous resin dispersion having a low viscosity. In addition, MW can be measured by a gel permeation chromatography (GPC) method.

  The MW of (b3 ′) is preferably 100 to 19,000, more preferably 200 to 14,000, and more preferably 300 to 9,000. Particularly preferably, it is 1,000 to 4,000, very preferably 1,500 to 3,800, and most preferably 2,000 to 3,500. The MW is preferably 100 or more, more preferably 1,000 or more in terms of obtaining sufficient surface active ability, and preferably 19,000 or less in terms of obtaining a stable aqueous resin dispersion having a low viscosity. In view of the above, 4,000 or less is preferable.

  In the above (b3 ′), the weight ratio of the structural units (b1), (b2) and added AO is preferably (1-5) / (0-99) / (0-99), More preferably (1-5) / (1-60) / (1-60).

  Specific examples of (b3 ′) include polyoxyalkylene ethers among the compounds exemplified in (b3) above.

  As a component of the reactive surfactant (B2), the above-described extender (b8) may be included as necessary.

The reactive surfactant (B0) of the present invention is an alkylene oxide adduct (b3 ″) as an addition reaction product comprising a monohydric phenol or a monovalent aromatic alcohol (b1) and, if necessary, a vinyl monomer (b2). Organic diisocyanate (b4), and diol and / or diamine (b5 ′) having a polyoxyalkylene chain as main components, and the terminal is a compound having an amino group, a hydroxyl group or a carboxyl group (B3). preferable. It is more preferable that the terminal is (B3 ′) which is a compound having an amino group or a hydroxyl group.
The alkylene oxides in the above (b1) and (b3 ″) are the same as those in the above (B1).

The reactive surfactant (B3 ′) is composed of one or more compounds represented by the following general formula (5) or (6).
Q-(-CONH-G-NHCO-J-) _m- OH (5)
Q - (- CONH-G- NHCO-J-) m -NH 2 (6)
In the formula, Q, G and J are the same as above. A plurality of G and a plurality of J may be the same or different. m is 1-20.

  The weight average molecular weight of (B3) is preferably 1,500 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000. The MW is preferably 1,500 or more from the viewpoint of obtaining sufficient surface active ability, and preferably 30,000 or less from the viewpoint of obtaining a stable aqueous resin dispersion having a low viscosity. In addition, MW can be measured by a gel permeation chromatography (GPC) method.

  The MW of (b3 ″) is preferably 1,000 to 4,000, more preferably 1,500 to 3,800, and particularly preferably 2,000 to 3,500. The MW is preferably 1,000 or more from the viewpoint of obtaining sufficient surface activity, and preferably 4,000 or less from the viewpoint of water resistance.

  In the above (b3 ″), the weight ratio of the structural units (b1), (b2) and added AO is preferably (1-5) / (0-99) / (0-99). More preferably, it is (1-5) / (1-60) / (1-60).

  Specific examples of (b3 ″) include polyoxyalkylene ethers among the compounds exemplified in (b3) above.

  It does not specifically limit as organic diisocyanate (b4), For example, what is illustrated above is mentioned.

The diol and / or diamine (b5 ′) having a polyoxyalkylene chain is preferably 20 to 100% by weight of the polyoxyethylene unit based on the weight of (b5 ′), from the viewpoint of the emulsifying power of (B0). More preferably, it contains 50 to 100% by weight, and particularly preferably 70 to 100% by weight.
Examples of (b5 ′) include polyoxyalkylene ethers having a terminal hydroxyl group and polyoxyalkylene ethers having a terminal amino group among the compounds exemplified in (b5) above.

  The MW of (b5 ′) is preferably 1,000 to 4,000, more preferably 1,500 to 3,800, and particularly preferably 2,000 to 3,500. The MW is preferably 1,000 or more from the viewpoint of obtaining sufficient surface active ability, and preferably 4,000 or less from the viewpoint of water resistance.

  As a component of the reactive surfactant (B3), the above-described extender (b8) may be included as necessary.

In the present invention, the method for producing the urethane resin (B1) is as follows:
(1) When the terminal is blocked with an isocyanate group, (b3) to (b5) and (b6) are subjected to a urethanation reaction by a usual method for producing a polyurethane resin (one-shot method or multistage method). It is obtained by preparing a polyurethane resin having one end at the NCO group and finally blocking the terminal isocyanate group with a blocking agent. The reaction temperature is usually 30 to 200 ° C, preferably 50 to 180 ° C. The reaction time is usually 0.1 to 30 hours, preferably 0.1 to 8 hours.
The 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 (B).

(2) When an epoxy group is added to the terminal, (b3) to (b5) and (b6) are subjected to a urethanization reaction by a method for producing a normal polyurethane resin (one-shot method or multistage method), It is obtained by producing a polyurethane resin having one end at the active hydrogen and finally reacting with a polyepoxy compound. The reaction temperature and reaction time may be the same as described above.
The use of the solvent may be the same as described above.

In the present invention, the production method of the reactive surfactant (B2) is (1) a method of producing an ordinary polyurethane resin (one-shot method or multistage method) when the terminal is blocked with an isocyanate group. (B3 ′), (b4), and (b6) are subjected to a urethanation reaction to produce a resin having an NCO group at one end, and finally, the terminal isocyanate group is blocked with a blocking agent. The reaction temperature and reaction time may be the same as described above.
The use of the solvent may be the same as described above.

(2) When an epoxy group is added to the terminal, it can be obtained by reacting (b3 ′) and (b7). The reaction temperature and reaction time may be the same as described above.
The reaction is preferably performed in a solventless system or in an organic solvent. As the organic solvent, those similar to the above can be used. The organic solvent is preferably removed by distillation or the like after producing (B).

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 (b4) is preferably 1: (0. 8 to 1.5), more preferably 1: (0.8 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 coating film from the obtained aqueous resin dispersion becomes good.

In the present invention, the production method of the reactive surfactant (B3) is as follows:
(1) Resin having (b3 ″), (b4), and (b5 ′) urethanated by a conventional method (one-shot method or multistage method) for producing a polyurethane resin, and one end of which is a hydroxyl group or an amino group Is obtained. The reaction temperature and reaction time may be the same as described above.
The use of the solvent may be the same as described above. If necessary, a carboxyl group may be introduced by a method such as reacting an acid anhydride (for example, succinic anhydride, acetic anhydride, phthalic anhydride, maleic anhydride, etc.) with a terminal hydroxyl group or amino group.

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 (b4) is preferably 1: (0. 6 to 0.95), more preferably 1: (0.7 to 0.9). When the NCO group equivalent ratio is 0.6 to 0.95, the obtained polyurethane resin has an appropriate molecular weight, and the water resistance of the coating film obtained from the obtained aqueous resin dispersion becomes good.

In the slurry paint of the present invention, the fine particles (A) comprise a resin (a1) containing active hydrogen and, if necessary, a curing agent (a2). (A1) and (a2) are dissolved in an organic solvent, for example. Then, they are mixed by melt kneading.
In the slurry paint of the present invention, the particle shape of the fine particles (A) may be indefinite or spherical, but spherical is preferred in terms of the smoothness and uniformity of the coating film. Here, the term “spherical” refers to a particle having a major axis / minor axis ratio in the range of 1.0 to 1.5.
In addition, the volume average particle size of (A) is preferably 0.5 μm or more, more preferably 0.8 μm or more, and most preferably 1.0 μm or more from the viewpoint of the amount of dispersant added and water resistance. From the viewpoint of the smoothness of the coating film derived from the melting, it is preferably 50 μm or less, more preferably 20 μm or less, and most preferably 10 μm or less. The particle size measurement method includes electron microscope measurement, sedimentation method, electrozone method, dynamic light scattering method, and the like, but measurement by the dynamic light scattering method is preferable because of suitability of the measurement particle size range.

  In the slurry paint of the present invention, 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: methanol, isopropanol, ethanol, n-propanol, etc., ketone solvents: acetone, methyl ethyl ketone, etc. are mentioned. The mixing ratio of the water and the water-miscible solvent is preferably 100/0 to 100/20, more preferably 100/0 to 100/5.

  In the slurry paint of the invention, examples of the organic solvent for dissolving the curing agent (a2) in the active hydrogen-containing resin (a1) as necessary include, for example, aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon systems. Solvents, halogen solvents, ester solvents or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these Is mentioned. Of these, ketone solvents or ether solvents are preferred.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, and tetralin.
Examples of the aliphatic or alicyclic hydrocarbon solvent include n-hexane, n-heptane, mineral spirit, cyclohexane and the like.
Examples of the halogen solvent include methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene.
Examples of the ester or ester ether solvent include ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol.
Examples of the amide solvent include dimethylformamide and dimethylacetamide.
Examples of the sulfoxide solvent include dimethyl sulfoxide.
Examples of the heterocyclic compound solvent include N-methylpyrrolidone.

In the present invention, as the resin (a1) having active hydrogen [alcoholic hydroxyl group, phenolic hydroxyl group, amino group, carboxylic acid group, phosphoric acid group, thiol group, etc.], for example, acrylic resin (a1-1), polyester Examples of the resin (a1-2), polyurethane resin (a1-3), and epoxy resin (a1-4) include those containing active hydrogen groups.
Among these, an acrylic resin (a1-1) is preferable.
The active hydrogen equivalent of (a1) is preferably 100 to 10,000, more preferably 100 to 5,000, and particularly preferably 100 to 2000.

As monomers constituting the acrylic resin (a1-1), acrylic acid, acrylic acid ester having no hydroxyl group, acrylamide, acrylonitrile, methacrylic acid, methacrylic acid ester having no hydroxyl group, etc. (a1-1-1), and Acrylic acid ester or methacrylic acid ester (a1-1-2) having a hydroxyl group, and other monomer (a1-1-3) as necessary.
The weight ratio of (a1-1-1), (a1-1-2) and (a1-1-3) in the acrylic resin (a1-1) is preferably (0-80) / (1-100) / (0-50), more preferably (1-50) / (1-50) / (0-20).
(A1-1) is produced by a known polymerization method such as solution polymerization, bulk polymerization or suspension polymerization, and the weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. More preferably, it is 3,000 to 20,000.
Examples of (a1-1-1) include (cyclo) alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, ethylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, cyclohexyl (meth) acrylate, etc.].
Among these, preferred are methyl (meth) acrylate and n-butyl (meth) acrylate.
(A1-1-2) is hydroxyalkyl (2 to 4 carbon atoms) (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Etc.
Of these, 2-hydroxyethyl (meth) acrylate is preferred.
Examples of (a1-1-3) include styrene and isobornyl (meth) acrylate. Among these, styrene is preferable.

  The polyester resin (a1-2) includes a low molecular polyol and / or a condensed polyester polyol obtained by reacting a polyalkylene ether diol having a molecular weight of 1000 or less and a polycarboxylic acid, or a polylactone diol obtained by ring-opening polymerization of a lactone. And polycarbonate diol obtained by reacting a low molecular diol with a carbonic acid diester of a lower alcohol (such as methanol).

Examples of the low molecular polyol include the low molecular diols exemplified for the above (b5-1).
Examples of the polyalkylene ether diol having a molecular weight of 1,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more thereof.

  Examples of the polycarboxylic acid include the dicarboxylic acids exemplified for the above (b5-2); examples of the lactone include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and a mixture of two or more thereof. .

  Polyesterification is carried out by a conventional method, for example, a low molecular polyol and / or a polyether polyol having a molecular weight of 1000 or less, a polycarboxylic acid or an ester-forming derivative thereof [for example, anhydride (maleic anhydride, phthalic anhydride, etc.), lower ester (Dimethyl adipate, dimethyl terephthalate, etc.), halide, etc.] or its anhydride and alkylene oxide (for example, ethylene oxide and / or propylene oxide) are reacted (condensed), and one component, polyol, is excess It can be produced by a method in which an active hydrogen group is left at the terminal by using it, or a method in which a lactone is added to an initiator (low molecular diol and / or polyether diol having a molecular weight of 1,000 or less).

  Specific examples of (a1-2) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly Examples include diethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, and polyhexamethylene carbonate diol. It is done.

  The ratio of the constituent components of the hydroxyl group-containing polyester is such that the ratio of polyol to polycarboxylic acid is 2/1 to 1/1, as the molar ratio [OH] / [COOH] of hydroxyl group [OH] to carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1. In the case of other components, the ratio is the same as the components are changed. The MW is 1,000 to 50,000, preferably 2,000 to 20,000, and more preferably 3,000 to 15,000.

Examples of the polyurethane resin (a1-3) include a polyaddition product of a polyol and a diisocyanate.
Specific examples of the diisocyanate include those exemplified above. Specific examples of the polyol include a compound having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen atom-containing polyfunctional compound and a mixture of two or more thereof.

  Examples of the active hydrogen atom-containing polyfunctional compound include polyhydric alcohol (a1-3-1), polyhydric phenols (a1-3-2), amines (a1-3-3), and polycarboxylic acid (a1-3). -4), phosphoric acids (a1-3-5), polythiol (a1-3-6) and the like.

  Examples of the polyhydric alcohol (a1-3-1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and bis (hydroxymethyl). ) Dihydric alcohols such as cyclohexane and bis (hydroxyethyl) benzene; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc. 3 to 8 valent polyhydric alcohols.

  Examples of the polyhydric phenols (a1-3-2) include bisphenols such as bisphenol A, bisphenol F, and bisphenol S in addition to polyhydric phenols such as pyrogallol, catechol, and hydroquinone.

  Examples of amines (a1-3-3) include ammonia, monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine. Piperazine, N-aminoethylpiperazine and other heterocyclic polyamines described in JP-B No. 55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, Aromatic polyamines such as xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine; and monoethanolamine, diethanolamine, triethanol Amines, such as alkanolamines such as triisopropanolamine.

  Examples of the polycarboxylic acid (a1-3-4) include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid.

  Examples of phosphoric acids (a1-3-5) include phosphoric acid, phosphorous acid, and phosphonic acid. Examples of the polythiol (a1-3-6) include polyvalent polythiol compounds obtained by a reaction between a glycidyl group-containing compound and hydrogen sulfide.

  Two or more of the above-mentioned active hydrogen atom-containing compounds can be used.

  Examples of AO added to the active hydrogen atom-containing compound include ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), and styrene oxide. , Α-olefin oxide, epichlorohydrin and the like.

AO may be used singly or in combination of two or more. In the latter case, both block addition (chip type, balance type, active secondary type, etc.) and random addition are mixed systems [things chipped after random addition: 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains distributed arbitrarily, and 0 to 30% by weight (preferably 5 to 25% by weight) of EO chains chipped at the molecular ends ] May be used.
Among these AOs, preferred are EO alone, PO alone, THF alone, combined use of PO and EO, and combined use of PO and / or EO and THF (in the case of combined use, random, block and mixed system of both).

  The addition of AO to the active hydrogen atom-containing compound can be carried out in the usual manner, without catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (especially in the latter half of AO addition). The reaction is carried out in one step or in multiple steps at normal pressure or under pressure.

  The degree of unsaturation of the polyol is preferably small, and is usually 0.1 meq / g or less, preferably 0.05 meq / g or less, more preferably 0.02 meq / g or less.

  The ratio of polyol and diisocyanate is 1/2 or more and less than 1/1, preferably 1 / 1.5 or more and less than 1/1, as the molar ratio [OH] / [NCO] of hydroxyl group [OH] and isocyanate group [NCO]. More preferably, it is 1 / 1.3 or more and less than 1 / 1.02. In the case of other components, the ratio is the same as the components are changed. The weight average molecular weight is 1,000 to 50,000, preferably 2,000 to 20,000, and more preferably 3,000 to 15,000.

  Examples of the epoxy resin (a1-4) include addition condensates of polyepoxide (a1-4-1) and polycarboxylic acid (a1-4-2). During this addition polymerization, a hydroxyl group containing an active hydrogen group is generated.

  Examples of the polycarboxylic acid (a1-4-2) include those exemplified above. Further, the polyepoxide (a1-4-1) may be aliphatic, alicyclic, heterocyclic or aromatic.

Examples of the aromatic polyepoxide (a1-4-1) include glycidyl ethers of polyhydric phenols, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, and bisphenol AD diglycidyl. Ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, 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'-dihydroxybiphenyl Diglycidyl ether, glycidyl ether of phenol or cresol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, obtained by condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols and polyglycidyl ethers of polyphenols obtained by condensation reaction of resorcin and acetone.
Furthermore, in the present invention, as the aromatic polyepoxide, tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, a glycidyl group-containing polyurethane obtained by reacting a polyol with the two reactants (pre) Also included are diglycidyl ethers of polymers and alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenol A.

  Examples of the heterocyclic polyepoxide (a1-4-1) include trisglycidylmelamine.

  Examples of the alicyclic polyepoxide (a1-4-1) include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4 -Epoxy-6-methylcyclohexylmethyl) butylamine and the like. Moreover, as an alicyclic type | system | group, the nuclear hydrogenation thing of the said aromatic polyepoxide compound is also included.

Examples of the aliphatic polyepoxide (a1-4-1) include polyglycidyl ethers of polyvalent aliphatic alcohols, polyglycidyl esters of polyvalent fatty acids, and glycidyl aliphatic amines.
Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether. , Pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.
Examples of the polyglycidyl ester of polyvalent fatty acid include diglycidyl adipate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
In the present invention, the aliphatic system also includes a (co) polymer of glycidyl (meth) acrylate.

  Of these, preferred is a condensate of bisphenol A diglycidyl ether and adipic acid. The MW is 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 20,000.

The curing agent (a2) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule, and examples thereof include the organic diisocyanates exemplified above and the modified products exemplified above. It is done.
Of these, preferred are HDI isocyanurate and IPDI isocyanurate.
Examples of the blocking agent include the above-described blocking agents and combinations of two or more thereof.

  The ratio of the active hydrogen-containing resin (a1) to the curing agent (a2) is from 1/1 to less than 2/1, preferably 1.2, as the molar ratio of the active hydrogen group of (a1) to the isocyanate group of (a2). / 1 or more and less than 1.8 / 1, more preferably 1.3 / 1 or more and less than 1.6 / 1.

  The curing agent (a2) may also be added while the solution of fine particles (A) or (A) is dispersed in an aqueous medium.

  Therefore, as an aspect of the slurry paint of the present invention, for example, in an aqueous medium, fine particles (A) composed of a resin (a1) having an active hydrogen group, and composed of a hydrophilic part and a hydrophobic part, an isocyanate group, a blocked isocyanate A water-dispersed slurry paint comprising a reactive surfactant (B) having at least one group selected from the group consisting of a group and an epoxy group in the hydrophilic portion; a curing agent (a2) in the water-dispersed slurry paint; Further, a water-dispersed slurry paint comprising: a fine particle (A) comprising an active hydrogen group-containing resin (a1) in an aqueous medium, comprising a hydrophilic part and a hydrophobic part, and comprising a group comprising an amino group, a hydroxyl group and a carboxyl group. Examples include a reactive surfactant (B0) having at least one selected group in the hydrophilic portion, and a water-dispersed slurry paint containing a curing agent (a2). It is possible.

  In the slurry paint of the present invention, the content of the reactive surfactant (B) or (B0) is the total weight of the fine particles (A) and the reactive surfactant (B) or the fine particles (A) and (B), respectively. Preferably it is 0.1-10 weight% with respect to the total weight of a reactive surfactant (B0), More preferably, it is 0.5-8 weight%, Most preferably, it is 1-5 weight%.

The resin content in the slurry paint of the present invention is preferably 20 to 75% by weight, more preferably 20 to 60% by weight. Moreover, the volume average particle diameter in this slurry coating material is 0.5-50 micrometers.
When the resin content is 20 to 75% by weight, the dispersibility of the fine particles (A) in water is good. Moreover, when the particle size of the fine particles (A) is 0.5 to 50 μm, there is no sedimentation of the particles in water, and the water volatilization and viscosity adjustment during baking are facilitated.

  As long as the effect of the present invention is not impaired, (B) or (B0) and other known emulsifiers or surfactants (nonionic emulsifiers and surfactants, various reactive emulsifiers and surfactants) if necessary. Can be used in combination. The amount of the other emulsifier and surfactant used in combination is usually 30% by weight or less, preferably 10% by weight or less, based on the total amount of the emulsifier or surfactant.

  In the slurry paint of the present invention, a known additive (C) (for example, a viscosity modifier, a reaction accelerator, a filler, a thickener, a heat or weather resistance stabilizer, a leveling agent, if necessary, depending on the intended application. An antifoaming agent, a preservative, a coloring agent, etc.) can be optionally contained.

  Examples of the viscosity adjusting agent include a polyether type polymer viscosity adjusting agent and a urethane-modified polyether type associative viscosity adjusting agent. The blending amount is from 0.05% to 10%, preferably from 0.1% to 5%, based on 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 from 0.05% to 5%, preferably from 0.1% to 3%, based on the slurry paint.

  Examples of the weather stabilizer include salicylic acid ultraviolet absorbers such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, 2- Benzotriazole ultraviolet absorbers such as (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2-ethylhexyl-2-cyano- Examples include 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. It is. The blending amount is 0.05% or more and 10% or less, 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 resin, such as low molecular polyethylene and low molecular polypropylene, Olefin copolymers, such as an ethylene-acryl copolymer and an ethylene-methacryl copolymer, (meth) acryl copolymer And polyvinylpyrrolidone. The blending amount is from 0.2% to 6%, 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 the inorganic pigment include titanium oxide, carbon black, chromium oxide, and ferrite. As organic pigments, azo pigments such as azo lake, monoazo, disazo and chelate azo, benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone And polycyclic pigments such as those of the above-mentioned types. Examples of the dye include nigrosine and aniline. The blending amount varies depending on the type of the colorant, but is 0.5% or more and 30% or less, 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.
(1) Solvent removal method [In the aqueous medium containing (B) or (B0), the resin (a1) and, if necessary, the curing agent (a2) are dissolved in the organic solvent described above, and the reaction vessel is used with a homomixer or the like. In order to leave water, the volume-average particle size is reduced by dispersing in water and, if necessary, reducing the pressure to 0.1 to 15 Torr while heating up to 100 ° C. Method of dispersing fine particles of 0.5 μm to 50 μm in water];
(2) A pulverized particle dispersion method [resin (a1), and if necessary, (a2) is melt-kneaded, cooled and pulverized to obtain fine particles having a volume average particle size of 0.5 to 50 μm (B) or (B0) And a method of dispersing in a reaction vessel with a disperser or the like];
Among the above, the method (1) is preferable.
The concentration of (a1) and, if necessary, (a2) in the production according to (1) in the organic solvent is 20 to 75% by weight, preferably 40 to 60% by weight.
The concentration of (a1) and (a2) in the dispersion according to the production methods (1) and (2) above is 5 to 70% by weight, preferably 30 to 60% by weight. 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.

  In the present invention, the reactive surfactant (B) or (B0) exhibits good surface activity and dispersion stability. At the same time, by baking after applying the dispersion, the surfactant is chemically bonded to the dispersion and taken into the film, and exhibits excellent water resistance and strength.

The 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.
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 film thickness of the coated object obtained by applying and baking the paint of the present invention is 10 μm or more and 150 μm or less, preferably 15 μm or more and 50 μm or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents wt%.

Production Example 1
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of 4-α-cumylphenol and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Co., Ltd.) and stirred. The system was replaced with nitrogen gas, 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 7MW of styrene added to 1 mol of 4-α-cumylphenol (MW900) (B0-1). B0-1 with EO added (EO content 45%; MW 1800) 22.1 parts, polyethylene glycol (MW 6,000) 73.7 parts, hexamethylene diisocyanate (hereinafter abbreviated as HDI) 4.1 parts, methyl ethyl ketone oxime (Hereinafter abbreviated as MEK oxime) 0.4 parts are reacted at 80 ° C. for 3 hours, polyoxyethylene chain MW 5,500, oxyethylene unit content 87 wt%, MW 30,000, hydrocarbon group carbon number 71 in the hydrophobic part , 100 parts of a reactive surfactant [B-1] containing a blocked isocyanate group of HLB 16.6 was obtained.

Production Example 2
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Example 1 [EO added to 2 mol of styrene added to 1 mol of 4-α-cumylphenol (EO content 20%) MW800] 5.9 parts, polyethylene glycol (MW4,000) 88.2 parts, HDI 3.7 parts, bisphenol A diglycidyl ether 2.2 parts were reacted at 80 ° C. for 3 hours to obtain a polyoxyethylene chain MW5. 500 parts of a reactive surfactant [B-2] containing 500, an oxyethylene unit content of 80% by weight, MW 30,000, a hydrocarbon group having 31 carbon atoms in the hydrophobic part and an epoxy group having an HLB of 18.0 were obtained.

Production Example 3
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Example 1 (7 mol of styrene added to 1 mol of 4-α-cumylphenol and EO added (EO content 80%) ); MW5000] 94.4 parts, IPDI 4.0 parts, 1.6 parts of MEK oxime are reacted at 80 ° C. for 3 hours, polyoxyethylene chain MW4,500, oxyethylene unit content 31% by weight, MW5,500, hydrophobic 100 parts of a reactive surfactant [B-3] containing 15 parts of a hydrocarbon group and 15 HLB6.2 blocked isocyanate group was obtained.

Production Example 4
8. Hydroxyl group-containing hydrocarbons obtained by the same Friedel-Crafts reaction as in Example 1 [7 mol of styrene added to 1 mol of phenol with EO added (EO content 45%); MW 1700] 5 parts, 84.6 parts of polyethylene glycol (MW1000), 1.7 parts of HDI, and 0.9 parts of MEK oxime were reacted at 80 ° C. for 3 hours to give a polyoxyethylene chain MW 1,000, an oxyethylene unit content of 84% by weight, MW 25 100 parts of a reactive surfactant [B-4] containing a blocked isocyanate group having a hydrocarbon group of 62,000 and a hydrophobic part of HLB of 16.4.

Production Example 5
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Example 1 [7 mol of styrene added to 1 mol of phenol, EO added (EO content 45%); MW 1700] 16. 9 parts, 79.7 parts of polyethylene glycol (MW4000), and 3.4 parts of HDMI were reacted at 80 ° C. for 3 hours, polyoxyethylene chain MW3,600, oxyethylene unit content 87 wt%, MW24,000, carbonization of hydrophobic part 100 parts of reactive surfactant [B-5] containing 62 hydrogen atoms and a hydroxyl group of HLB17.2 was obtained.

Production Example 6
Hydroxyl group-containing hydrocarbons obtained by the same Friedel-Crafts reaction as in Example 1 [7 mol of styrene added to 1 mol of phenol with EO added (EO content 45%); MW 1700] 42. 2 parts, 50.0 parts of polyethylene glycol (MW1000) and 8.2 parts of HDI are reacted at 80 ° C. for 3 hours, polyoxyethylene chain MW1,150, oxyethylene unit content 72% by weight, MW12,000, carbonization of hydrophobic part 100 parts of reactive surfactant [B-6] containing a hydrogen group having 62 carbon atoms and a hydroxyl group of HLB16.2 were obtained.

Production Example 7
Hydroxyl group-containing hydrocarbons obtained by the same Friedel-Crafts reaction as in Example 1 [7 mol of styrene added to 1 mol of phenol with EO added (EO content 45%); MW 1700] 21. 2 parts, polyethylene glycol (MW3000) 74,7 parts, and HDMI 4.1 parts are reacted at 80 ° C. for 3 hours, polyoxyethylene chain MW2,700, oxyethylene unit content 84 wt%, MW 18,000, carbonization of hydrophobic part 100 parts of a reactive surfactant [B-7] containing a hydroxyl group having 62 carbon atoms and a HLB of 16.8 were obtained.

Comparative production example 1
Polyoxyalkylene monool [styrene 7 mol addition 4-α-cumylphenol added with ethylene oxide; MW 1,500] 19.3 parts, polyethylene glycol (MW 6,000) 77.4 parts and HDI 3.3 parts Was reacted at 80 ° C. for 3 hours until the NCO content became 0% to obtain 100 parts of a surfactant [B′-8].

Comparative production example 2
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of 4-α-cumylphenol and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Co., Ltd.) and stirred. The system was replaced with nitrogen gas, and the temperature was raised to 90 ° C. At the same temperature, 410 parts of ethanol block product of 3-isopropenyl-α, α-dimethylbenzyl isocyanate was added dropwise over 3 hours, and further reacted at the same temperature for 5 hours. This was cooled to 30 ° C., and the catalyst was filtered off to add 1 mol of 3-isopropenyl-α, α-dimethylbenzyl isocyanate to 1 mol of 4-α-cumylphenol (MW1900) (B0-2) ) Was obtained 220 parts. B0-2 with EO added (EO content 45%; MW 3400) 22.1 parts, polyethylene glycol (MW 6,000) 73.7 parts, HDI 4.1 parts were reacted at 80 ° C. for 3 hours to give polyoxyethylene Reactive surfactant containing chain MW 5,400, oxyethylene unit content 86% by weight, MW 15,000, hydrocarbon group hydrocarbon number 71 in hydrophobic part, blocked isocyanate group of HLB16.2 in hydrophobic part [B′- 9] 100 parts were obtained.

Preparation of Acrylic Hydroxy Functional Resin 250 parts of xylene were placed in a reactor and heated to 100 ° C., then a mixture as shown below was added dropwise for about 3 hours. The reaction during that time was performed in a nitrogen atmosphere. After completion of the dropping, the reaction was continued at 100 ° C. for 2 hours.
(1) Styrene 23 parts (2) Methyl methacrylate 23 parts (3) Butyl acrylate 20 parts (4) Hydroxyethyl acrylate 33 parts (5) Peroxy D (manufactured by NOF Corporation, peroxide) 1 part After completion of the reaction, The organic solvent and residual monomer were removed by distillation under reduced pressure, and then vacuum drying was performed to obtain an acrylic hydroxy functional resin (acrylic resin 1) having a hydroxyl group equivalent of 420 and a number average molecular weight of 12,000.
59 parts of the acrylic resin 1 obtained above and 41 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijoule) were kneaded at 100 ° C. using a heating kneader and pulverized to about 5 μm to obtain a volume average particle size. Acrylic resin 2 having a long diameter / short diameter ratio of 1.2 was obtained.

Preparation of polyester resin In a reactor, 200 parts of neopentyl glycol, 93 parts of ethylene glycol and 355 parts of terephthalic acid were charged, and the reaction was allowed to proceed for 2 hours while heating to 230 ° C. and distilling off the generated water. Thereafter, 0.2 part of dibutyltin oxide is added, and the reaction is continued until the acid value becomes 0.5 or less, so that the number average molecular weight 7000, hydroxyl group having hydroxyl groups at both ends, used in the coating film of the present invention is used. A polyester resin (polyester resin 1) having a value of 16.5 mgKOH / g and a hydroxyl group equivalent of 926 was obtained.
93 parts of the polyester resin 1 obtained above and 7 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumidu) were kneaded using a heating kneader at 100 ° C., and then pulverized to about 5 μm, and the volume average particle diameter A polyester resin 2 having a long diameter / short diameter ratio of 1.2 was obtained.

Preparation Examples of Dispersions Reactive surfactants [B-1] to [B-7] obtained in Production Examples 1 to 7, surfactant [B′-8] obtained from Comparative Production Example 1, and comparison Surfactant [B′-9] obtained from Production Example 2, Low molecular weight surfactant [B′-10] (EO adduct of octylphenol, number average molecular weight 1,000), PVA [B′-11] Three parts each of (saponified polyvinyl alcohol, degree of polymerization 1,700, degree of saponification 88%) were dispersed in 100 parts of water to obtain a dispersion. Let this be dispersion 1 to dispersion 10.

Example 1
In a beaker, 59 parts of acrylic resin 1, 41 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijoule), and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 1. Using an ultradisperser (manufactured by Yamato Kagaku), mixing was performed at a rotation speed of 9,000 rpm for 1 minute, so that the volume average particle diameter was 5 μm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at room temperature and reduced pressure for 10 hours. Next, 0.1 part of urethanization catalyst [“TEDA”, manufactured by Tosoh Corporation], light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.] 0.1 part, viscoelasticity imparting agent [“SN thickener-651” , Manufactured by San Nopco Co., Ltd.] was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 4.7 μm.

Example 2
A water-dispersed slurry paint in the same manner as in Example 1 except that the dispersion 2 is used instead of the dispersion 1, and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is 12,000 rpm. Got. The volume average particle diameter of the dispersed particles was 3.1 μm.

Example 3
A water-dispersed slurry paint in the same manner as in Example 1, except that the dispersion 3 is used instead of the dispersion 1, and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is 14,000 rpm for 2 minutes. Got. The volume average particle diameter of the dispersed particles was 2.4 μm.

Example 4
A water-dispersed slurry paint in the same manner as in Example 1 except that the dispersion 4 is used instead of the dispersion 1, and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is 16,000 rpm for 2 minutes. Got. The volume average particle diameter of the dispersed particles was 1.8 μm.

Example 5
A water-dispersed slurry paint in the same manner as in Example 1, except that the dispersion 5 is used instead of the dispersion 1, and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is 16,000 rpm for 2 minutes. Got. The volume average particle diameter of the dispersed particles was 1.7 μm.

Example 6
A water-dispersed slurry paint in the same manner as in Example 1 except that the dispersion 6 is used in place of the dispersion 1, and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is 16,000 rpm for 2 minutes. Got. The volume average particle diameter of the dispersed particles was 1.9 μm.

Example 7
A water-dispersed slurry paint in the same manner as in Example 1 except that the dispersion liquid 7 is used instead of the dispersion liquid 1 and the stirring condition in the ultradisperser (manufactured by Yamato Kagaku) is set to 16,000 rpm for 2 minutes. Got. The volume average particle diameter of the dispersed particles was 2.3 μm.

Comparative Examples 1-4
A water-dispersed slurry paint was obtained in the same manner as in Example 1 except that the dispersions 8 to 11 were used instead of the dispersion 1. Comparative Example 1: Volume average particle diameter of dispersed particles is 4.8 μm, Comparative Example 2: Volume average particle diameter of dispersed particles is 5.1 μm, Comparative Example 3: Volume average particle diameter of dispersed particles is 4.9 μm, Comparative Example 4: Dispersion The volume average particle diameter of the particles was 4.8 μm.

Example 8
100 parts of acrylic hydroxy functional resin fine powder (acrylic resin 2) obtained above is added to 100 parts of dispersion 1 obtained by the preparation example of dispersion, and Ultradisperser (manufactured by Yamato Kagaku) is added. Used and mixed for 1 minute at 9,000 rpm. Next, 0.1 part of a urethanization catalyst [“TEDA”, manufactured by Tosoh] and 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.] were added, and the volume average particle diameter of the dispersed particles was 7 μm. A desired water-dispersed slurry paint was obtained.

Example 9
A water-dispersed slurry paint was obtained in the same manner as in Example 8, except that the dispersion 2 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 7 μm.

Example 10
A water-dispersed slurry paint was obtained in the same manner as in Example 8 except that the dispersion 5 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 7 μm.

Comparative Examples 5-8
A water-dispersed slurry paint was obtained in the same manner as in Example 8 except that the dispersions 8 to 11 were used instead of the dispersion 1. Comparative Example 5: Volume average particle size 7 μm of dispersed particles, Comparative Example 6: Volume average particle size 7 μm of dispersed particles, Comparative Example 7: Volume average particle size 7 μm of dispersed particles, Comparative Example 8: Volume average particle size of dispersed particles It was 7 μm.

Example 11
In a beaker, 93 parts of polyester resin 1, 7 parts of MEK oxime-blocked HDI trimer (manufactured by Asahi Kasei, Sumijoule), and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 1. Using an ultradisperser (manufactured by Yamato Kagaku), mixing was performed at a rotation speed of 9,000 rpm for 1 minute, and the volume average particle diameter was adjusted to 5 μm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at room temperature and reduced pressure for 10 hours. Next, 0.1 part of urethanization catalyst [“TEDA”, manufactured by Tosoh Corporation], light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.] 0.1 part, viscoelasticity imparting agent [“SN thickener-651” [Manufactured by San Nopco Co., Ltd.] 3.0 parts were added to obtain a target water-dispersed slurry paint having a volume average particle diameter of 5.1 μm of dispersed particles.

Example 12
A water-dispersed slurry paint was obtained in the same manner as in Example 11 except that the dispersion 2 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 4.9 μm.

Example 13
A water-dispersed slurry paint was obtained in the same manner as in Example 11 except that the dispersion 5 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 4.2 μm.

Comparative Examples 9-12
A water-dispersed slurry paint was obtained in the same manner as in Example 11 except that the dispersions 8 to 11 were used instead of the dispersion 1. Comparative Example 9: Volume average particle size of dispersed particles 4.8 μm, Comparative Example 10: Volume average particle size of dispersed particles 4.9 μm, Comparative Example 11: Volume average particle size of dispersed particles 5.1 μm, Comparative Example 12: Dispersed The volume average particle diameter of the particles was 4.8 μm.

Example 14
100 parts of the polyester-based hydroxy functional resin fine powder (polyester resin 2) obtained above is added to 100 parts of dispersion 1 obtained by the preparation example of dispersion, and Ultradisperser (manufactured by Yamato Kagaku) is added. Used and mixed for 1 minute at 9,000 rpm. Next, 0.1 part of a urethanization catalyst [“TEDA”, manufactured by Tosoh] and 0.1 part of a light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.] were added, and the volume average particle diameter of the dispersed particles was 7 μm. A desired water-dispersed slurry paint was obtained.

Example 15
A water-dispersed slurry paint was obtained in the same manner as in Example 14 except that the dispersion 2 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 7 μm.

Example 16
A water-dispersed slurry paint was obtained in the same manner as in Example 14 except that the dispersion 5 was used instead of the dispersion 1. The volume average particle diameter of the dispersed particles was 7 μm.

Comparative Examples 13-16
A water-dispersed slurry paint was obtained in the same manner as in Example 14 except that the dispersions 8 to 11 were used instead of the dispersion 1. Comparative Example 13: Volume average particle size 7 μm of dispersed particles, Comparative Example 14: Volume average particle size 7 μm of dispersed particles, Comparative Example 15: Volume average particle size 7 μm of dispersed particles, Comparative Example 16: Volume average particle size of dispersed particles It was 7 μm.

  Each water-dispersed slurry paint obtained by the above method was evaluated by the following test method. The results are shown in Table 1, Table 2, Table 3 and Table 4. In the table, “particle size” represents the volume average particle size of the dispersed particles.

(Preparation of test piece)
A 0.8mm thick cold-rolled steel sheet treated with zinc phosphate is coated with an epoxy resin-based cationic electrodeposition paint (20μm) and cured by heating at 170 ° C for 30 minutes. A test plate was obtained by spray coating (30 μm) and heating and curing at 140 ° C. for 30 minutes. The obtained water-dispersed slurry paint was spray-coated on the test plate, pre-baked at 60 ° C. for 10 minutes, and then baked and dried at 150 ° C. for 20 minutes to obtain a coating film having a thickness of about 40 μm.
(Test method)
<Measurement of Fischer hardness>: The surface hardness of the coating film obtained above was measured with a Fischer hardness meter (Fischer scope H100V manufactured by Fisher Instruments). (Loading 0.4-100mN, pushing depth 5μm)
This test method can quantify the coating film hardness with high accuracy, and can evaluate many factors of coating film strength such as indentation hardness and Young's modulus in one test.
The coating film strength can be evaluated by measuring the surface hardness.
<Evaluation of acid rain resistance>: 0.4 g of 30% sulfuric acid aqueous solution was dropped onto the coating film obtained above, heated at 80 ° C. for 30 minutes in a circulating dryer, washed with water, and the coated surface was visually observed. evaluated.
○: No change is observed on the coated surface.
(Triangle | delta): A trace of dripping is recognized a little.
X: Spots, whitening or blisters are remarkably observed in the dropping mark.
<Measurement of dissolution rate>: About 10 g of the coating film obtained above was immersed in water at 25 ° C. for 1 hour, and the film after water immersion was dried by heating at 60 ° C. for 1 hour in a circulating dryer. Compared with the weight of the film before immersion, the weight reduction rate was measured and used as the dissolution rate.
<Evaluation of water resistance>: The coating film obtained above was immersed in water at 40 ° C. for 10 days, and the film after water immersion was visually evaluated.
○: No change is observed in the coating film.
Δ: Some whitening is observed in the coating film.
X: Whitening is remarkably recognized in the coating film.

  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.

Claims (14)

In the aqueous medium, at least one selected from the group consisting of fine particles (A) comprising a resin (a1) having an active hydrogen group, and a hydrophilic part and a hydrophobic part, and comprising an isocyanate group, a blocked isocyanate group and an epoxy group A water-dispersed slurry paint comprising a reactive surfactant (B) having a group in a hydrophilic part. The water-dispersed slurry paint according to claim 1, further comprising a curing agent (a2). The water-dispersed slurry paint according to claim 1 or 2, wherein the reactive surfactant (B) contains a hydrophobic part having a hydrocarbon group having 6 to 100 carbon atoms and containing an aromatic ring. The water-dispersed slurry paint according to any one of claims 1 to 3 , wherein the reactive surfactant (B) contains an oxyethylene group in an amount of 20 wt% to 97 wt% with respect to the weight of (B) . The reactive surfactant (B) comprises a hydrophilic part having a polyoxyethylene chain, the polyoxyethylene chain has a weight average molecular weight of 1,000 or more and 4,000 or less, and the reactive surfactant The water-dispersed slurry paint according to any one of claims 1 to 4 , wherein the weight average molecular weight of (B) is from 1,500 to 30,000. The water-dispersed slurry paint according to any one of claims 1 to 5 , wherein the reactive surfactant (B) comprises one or more compounds represented by the following general formula (1) or (2).
Q-(-CONH-G-NHCO-J-) _m -CONH-G-NHCO-Y (1)
Q-(-CONH-G-NHCO-J-) _m -Z (2)
[In the formula, Q is a residue of monohydric phenol or monovalent aromatic alcohol (b1) or its alkylene oxide adduct (b3) , G is a residue of organic diisocyanate (b4), J is a poly A diol and / or diamine (b5) residue having an oxyalkylene chain, Y a residue of a blocking agent (b6), and Z a residue of a polyepoxy compound (b7). A plurality of G and a plurality of J may be the same or different. m is 1-20. ] In the general formulas (1) and (2), the reactive surfactant (B) is Friedel Crafts of monohydric phenol or monovalent aromatic alcohol (b1) and vinyl monomer (b2). The residue of the addition reaction product by reaction or the alkylene oxide addition product thereof, wherein G, J, Y, Z and m are composed of one or more of the same compounds as described above. The water-dispersed slurry paint described . The water-dispersed slurry paint according to any one of claims 1 to 5 , wherein the reactive surfactant (B) comprises one or more compounds represented by the following general formula (3) or (4).
Q'-CONH-G-NHCO-Y (3)
Q'-Z (4)
[In the formula, Q ′ is a residue of an alkylene oxide adduct (b3 ′) of monohydric phenol or monovalent aromatic alcohol (b1), G is a residue of organic diisocyanate (b4), and Y is , Z represents a residue of the blocking agent (b6), and Z represents a residue of the polyepoxy compound (b7). ] In the general formulas (3) and (4), the reactive surfactant (B) is a Friedel of monovalent phenol or monovalent aromatic alcohol (b1) and vinyl monomer (b2). The aqueous dispersion according to claim 1, which represents a residue of an alkylene oxide adduct of an addition reaction product by a Crafts reaction, wherein G, Y, and Z are one or more of the same compounds as described above. Slurry paint. The water-dispersed slurry paint according to any one of claims 1 to 9 , wherein the resin (a1) having an active hydrogen group is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin. The water-dispersed slurry paint according to any one of claims 1 to 10 , wherein the volume average particle size of the fine particles (A) is 0.5 µm or more and 50 µm or less. The water-dispersed slurry paint according to any one of claims 1 to 11 , wherein the fine particles (A) have a spherical shape with a major axis / minor axis ratio of 1.0 to 1.5. The water-dispersed slurry paint according to any one of claims 1 to 12 , wherein the fine particles (A) are obtained by dispersing a solvent solution of the resin (a1) having active hydrogen in water and removing the solvent. Claim 1 aqueous dispersion slurry coating material according to any one of 13 was applied, the coating film obtained by baking.