JP4870930B2 - Water-dispersed slurry paint with excellent storage stability - Google Patents

Description

  The present invention relates to a slurry coating composition. More specifically, the present invention relates to a slurry coating composition having excellent storage stability of a resin dispersed in water, and water resistance and strength of a cured coating film after baking.

  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 over a long period of time and to stably disperse the fine particles in water. Used (Patent Document 1). Examples of the surfactant to be used include an anionic surfactant (Patent Document 2), a non-blocking surfactant having a hydrophobic portion at one end (Patent Document 3), and the like.

JP 2001-220544 A JP 2004-530026 A JP 2003-160755 A

  However, anionic surfactants have excellent storage stability, but have a problem that water resistance deteriorates. In addition, the non-blocking nonionic surfactant having a hydrophobic portion at one end has a problem that the stability in a dispersed state at the time of storage is not sufficient. Accordingly, an object of the present invention is to provide a water-dispersed slurry paint with improved storage stability and water resistance, in which the above problems are improved.

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 relates to a resin having at least one reactive functional group selected from the group consisting of alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxylic acid groups, phosphoric acid groups, and thiol groups in an aqueous medium ( A water-dispersed slurry paint comprising a fine particle (A) having a volume average particle diameter of 0.5 μm to 50 μm and a surfactant (B) having the following structure:
At least two hydrophobic units (U) having a hydrocarbon group having 6 to 100 carbon atoms having 1 to 12 aromatic rings as repeating units, and at least one hydrophilic unit (W) having an oxyethylene chain as repeating units Surfactant (B) having a repeating structure and both ends being a hydrophobic part (U): However, the compatibility parameter of the resin (a1) and the phase of the hydrophobic part (U) of the surfactant (B) A reactive interface having a solubility parameter difference of 0 to 1 and the surfactant (B) having at least one group selected from the group consisting of a carboxyl group, an amino group, an isocyanate group, a blocked isocyanate group and an epoxy group It is an activator.

  The water-dispersed slurry paint of the present invention exhibits excellent storage stability and excellent coating film properties such as water resistance of the cured coating film.

Hereinafter, the present invention will be described in detail.
The surfactant (B) in the present invention has a repeating structure of a hydrophobic part (U) unit and a hydrophilic part (W) unit, and both ends are hydrophobic parts (U). The structure is preferably a triblock type of hydrophobic part (U) -hydrophilic part (W) -hydrophobic part (U) from the viewpoint of adsorptivity to resin particles. By having a repeating structure of (U) and (W), the number of adsorption points to the resin particles of (B) is increased, and the adsorbability is improved to show excellent storage stability and a cured coating. Excellent film properties such as water resistance of the film. Furthermore, the adsorption | suction improvement can be anticipated further by making both ends into which a chain | strand movement is free into a hydrophobic part (U).

  The hydrophobic part (U) contains an aromatic ring and has 6 to 100 carbon atoms, preferably 10 to 50 carbon atoms, more preferably 15 to 40 carbon atoms. The number of aromatic rings to be contained is 1 to 12, preferably 2 to 10 and more preferably 4 to 8 from the viewpoint of adsorptivity to resin particles. When the number of carbon atoms in (U) is 5 or less, the adsorptivity to the resin particles is poor and the dispersibility is deteriorated. When the number of carbon atoms in (U) is 101 or more, the solubility in water is poor and the dispersibility is deteriorated. When (U) has no aromatic ring, the adsorptivity to the resin particles is poor and the dispersibility is deteriorated. When the number of aromatic rings contained in (U) is 13 or more, the solubility in water is poor and the dispersibility is deteriorated.

  The difference in the compatibility parameter (hereinafter referred to as SP value) between the hydrophobic part (U) and the resin (a1) is preferably 0 to 1, and preferably 0 to 0.5 from the viewpoint of adsorptivity. More preferably, it is 0-0.3.

The 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 ).
In addition, ΔH and V are the total heat of molar evaporation of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153)” (ΔH ) And the sum of molar volumes (V).
Those having a close numerical value are easy to mix with each other (high compatibility), and those having a close numerical value are indices that indicate that they are difficult to mix.

  Examples of the hydrophobic part (U) include a residue obtained by removing a hydroxyl group from phenols, a compound obtained by adding a vinyl monomer to these compounds (U1), and a hydroxyl group from bisphenols (such as bisphenol A, bisphenol S, and bisphenol F). Residues obtained by removing the hydroxyl group from the removed residues and those obtained by adding vinyl monomers to these compounds (U2), phenol novolak resins (hydroxyl valences 1 to 8), and cresol novolac resins (hydroxyl valences 1 to 8) And a group obtained by adding a vinyl monomer to these compounds (U3), a residue obtained by removing a hydroxyl group from an aromatic alcohol, and a compound obtained by adding a vinyl monomer to these compounds (U4).

Specific examples include (U1): phenyl group, alkyl (C1-18) phenyl group (for example, nonylphenol, dodecylphenol, octylphenol, etc.), styrenated (addition mole number 1-10) phenyl group, alkylarylated phenol. (For example, cumylphenol), styrenation (addition mole number 1 to 10) cumenyl (isopropylphenyl) group and the like.
(U2): Bisphenyl group (bisphenol A, bisphenol S, bisphenol F, etc.), styrenated (addition mole number 1-10) bisphenyl group, and the like.
(U3): Residue obtained by removing hydroxyl group from phenol novolac resin (hydroxyl valence 1-8), styrenated (addition mole number 1-10), hydroxyl group removed from phenol novolac resin (hydroxyl valence 1-8) Residues obtained by removing hydroxyl groups from cresol novolak resins (hydroxyl valences 1 to 8), styrenated (added moles 1 to 10) cresol novolak resins (hydroxyl valences 1 to 8) from hydroxyl groups Residue.
(U4): 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 hydrophilic part (W) has an oxyethylene chain. The oxyethylene chain is composed of an oxyethylene group, and the oxyethylene chain in (W) may be a copolymer of an oxyalkylene group other than the oxyethylene group, for example, an oxypropylene group and the oxyethylene group, The copolymerization molar ratio of oxyalkylene groups other than oxyethylene groups is preferably 20 mol% or less, more preferably 10 mol% or less.
In the present invention, an oxyethylene chain having a copolymerization molar ratio of oxyalkylene groups other than oxyethylene groups of 20 mol% or less is considered to form a hydrophilic portion (W).

The content of the oxyethylene group is preferably 20% by weight or more, more preferably 25% by weight or more, particularly preferably 30% by weight or more, preferably 97% by weight or less, based on the weight of the surfactant (B). More preferably, it is 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.
In the above (B), the oxyethylene group is preferably 70% by weight or more, more preferably 75% by weight or more, particularly preferably 80% by weight or more, preferably 99% by weight based on the weight of the hydrophilic part (W). % Or less, more preferably 98% by weight or less, 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.

Examples of the hydrophilic portion (W) include the following groups (W1) and (W2) bonded to the phenolic or alcoholic hydroxyl group of the hydrophobic portion (U).
(W1): a group obtained by removing two hydrogens from polyoxyethylene ether, (W2): a group obtained by removing two hydrogens from a urethane resin composed of polyoxyethylene ether and diisocyanate.

  The weight ratio (W / U) of the hydrophilic part (W) to the hydrophobic part (U) in the above (B) is preferably 0.03 to 4.0, more preferably 0.05 to 3.0, particularly preferably. 0.07 to 2.3.

From the viewpoint of the hydrophilic group-hydrophobic group balance (hereinafter referred to as HLB) of (B) above, the ability to emulsify the ethylenically unsaturated monomer and the fine particles are dispersed to form a stable aqueous dispersion or aqueous emulsion. 5-20 are preferable and 7-20 are more preferable. The adjustment of the HLB in the above (B) can be performed, for example, by adjusting the type and content of the hydrophobic group in the above (B) and adjusting the type and content of the hydrophilic group. 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 the inorganic value are determined from the type and content of the hydrophobic group and the type and content of the hydrophilic group in (B) above. Obtain HLB by the following formula.
HLB = 10 × (inorganic / organic)

  The weight average molecular weight of the polyoxyethylene chain in the surfactant (B) is preferably 1,000 to 4,000, more preferably 1,500 to 3,800, and particularly preferably 2,000 to 3 from the viewpoint of water resistance. , 500.

The surfactant (B) is a reactive surfactant (B0) having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, a blocked isocyanate group, and an epoxy group. Those having a hydroxyl group, a blocked isocyanate group, and an amino group are more preferred from the viewpoint of reactivity. (B) having low compatibility with the resin (a1) containing a reactive functional group is directly bonded to (a1), so that compatibility with the coating film is improved, excellent coating film strength is exhibited, and curing is performed. Excellent coating film properties such as water resistance of the coated film. In addition, when the paint is stored, the dispersion stability of the resin is excellent.
The reactive functional group can be introduced into the surfactant (B) by a known method such as a method using a monomer having the functional group, as will be exemplified later.

  Moreover, it is preferable that surfactant (B) of this invention is surfactant (B1) which is a urethane resin. The above (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 poly It is a urethane resin mainly composed of a diol having an oxyethylene chain and / or a diamine (b5). (B1) may further use an extender (b6) as necessary.

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

Triblock Q-CONH-G-NHCO-J-CONH-G-NHCO-Q (1)
Multi-block Q-(-CONH-G-NHCO-J-CONH-G-NHCO-Q'-CONH-G-NHCO-J-CONH-G-NHCO) _m- Q (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 its alkylene oxide adduct (b3), and Q ′ is G is a residue of an addition reaction product consisting of a divalent aromatic alcohol or a divalent phenol or the like (b1 ′) and, if necessary, a vinyl monomer (b2) or its alkylene oxide adduct (b3 ′), In the organic diisocyanate (b4) residue, J represents the residue of a diol and / or diamine (b5) having a polyoxyethylene chain. A plurality of G and a plurality of J may be the same or different. m is preferably 1 to 3, more preferably 1.

  The weight average molecular weight (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 3,000. ~ 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, cumyl). Phenol, etc.), monoalkyl (C 1-18) ethers of bisphenols (eg monomethyl ether of bisphenol A, monobutyl ether of bisphenol A, monobutyl ether of bisphenol S), aromatic alcohols (eg benzyl alcohol, etc.) and Examples thereof include a mixture of two or more of the above. Of these, preferred are phenol and cumylphenol.

The (b1 ′) is not particularly limited, and for example, divalent aromatic alcohols and divalent phenols can be used. Specific examples of the divalent phenols include monocyclic divalents such as catechol, resorcinol and hydroquinone; condensed divalents such as dihydroxynaphthalene and the like; bisphenols such as bisphenol A, bisphenol F, bisphenol S, Dihydroxy diphenyl ether, dihydroxy diphenyl thioether and the like; and binaphthol; and alkyl (carbon number 1 to 10) or halogen (chlorine, bromine, etc.) substituted products thereof (for example, brominated bisphenol A). Examples of the divalent aromatic alcohol include HOCH ₂ C ₆ H ₄ CH ₂ OH. Of these, bisphenol A, bisphenol F, and bisphenol S are preferred.

As the vinyl monomer (b2), for example, a vinyl monomer having a functional group, an aliphatic vinyl hydrocarbon, an alicyclic vinyl hydrocarbon, and an aromatic vinyl hydrocarbon can be used.
Examples of the vinyl monomer having a functional group include 2-hydroxyethyl methacrylate having a hydroxyl group, 3-isopropenyl-dimethylbenzyl isocyanate (hereinafter abbreviated as TMI) having an isocyanate group, and a vinyl monomer obtained by blocking this with MEK oxime ( (Hereinafter abbreviated as MEK oxime block of TMI), 2-aminoethyl methacrylate having an amino group, (meth) acrylic acid having a carboxyl group are aliphatic vinyl hydrocarbons such as 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 alicyclic vinyl Examples of the hydrocarbons include cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, and ethylidenebicycloheptene. Examples of the aromatic vinyl hydrocarbon include styrene, α-methylstyrene, Vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, trivinylbenzene Etc.
Of these, preferred are 2-hydroxyethyl methacrylate, TMI, MEK oxime block of TMI, 2-aminoethyl methacrylate, methacrylic acid and styrene.

In the above (b3) and (b3 ′), 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 the above Or a mixture of two or more thereof. 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. In the present invention, when AO is other than EO, the hydrophobic portion (U) is used, and when EO is a copolymer of AO other than EO, the number of moles of EO is 80% of the total number of moles of AO. If it is more than the above, it is regarded as a hydrophilic part (W), and if it is less than 80%, it is regarded as a hydrophobic part (U).

  The MW of (b3) and (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 to 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) and (b3 ′), the weight ratio of the structural unit (b1) or (b1 ′), (b2) and the added AO is preferably (1-5) / (0-99). ) / (0 to 99), more preferably (1 to 5) / (1 to 60) / (1 to 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.
Specific examples of (b3 ′) include, for example, styrenated (1 to 10 mol addition) catechol EO addition (1 to 25 mol), styrenated (1 to 10 mol addition) bisphenol A EO addition (1 to 25). Mol) product.

In (b3) and (b3 ′), the method of adding (b1), (b1 ′), or (b2) 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,
(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 aromatic aliphatic 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] A phosgenated product of: a polyallyl polyisocyanate (PAPI), etc.], and these blocked isocyanate compounds.
Of these, preferred are HDI, TDI and IPDI.

The diol and / or diamine (b5) having a polyoxyethylene 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 said (b5-1), the compound of the structure which EO added to low molecular diol or dihydric phenol, a mixture of these 2 or more types, etc. can be used, for example.

  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 Ethylene oxide adducts, etc.], dimethylolpropionic acid having a carboxyl group, and a mixture of two or more thereof.

  It does not specifically limit as said dihydric phenol, For example, what was illustrated above is mentioned.

  As the above (b5-2), for example, among the condensed polyester diols obtained by reacting the above (b5-1) having a MW of 1000 or less with a dicarboxylic acid and / or a low molecular diol, the polyoxyethylene unit is as described above. And the like.

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 the above (b5) is preferably 1,500 to 4,000. More preferably, it is 1,700-4,000, Most preferably, it is 2,000-4,000. The MW is preferably 1,500 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 surfactant (B1), an extender (b6) may be included as necessary. As (b6), 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] Formula diamines (for example, isophorone diamine, 4,4′-diaminodicyclohexylmethane, etc.), aromatic diamines having 6 to 15 carbon atoms (for example, 4,4′-diaminodiphenylmethane, etc.), etc .; monoalkanolamines (for example, 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.

  In the present invention, the above (B1) is obtained by subjecting the above (b3) to (b5) and (b6) to a urethanization reaction by a usual method for producing a polyurethane resin (one-shot method or multistage method). 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).

  The surfactant (B1) is a reactive surfactant (B10) having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, a blocked isocyanate group and an epoxy group. For example, it can be obtained by using dimethylolpropionic acid which is a low molecular diol containing a carboxyl group in (b3) and / or (b5) in (B1) above. Alternatively, it can be obtained by using 2-hydroxyethyl methacrylate, TMI, TMI oxime block of MEK, 2-aminoethyl methacrylate, or methacrylic acid, which is a vinyl monomer containing a functional group in (b2).

  In the slurry paint of the present invention, the fine particles (A) comprise a resin (a1) containing a reactive functional group and, if necessary, a curing agent (a2). (A1) and (a2) are dissolved in an organic solvent, for example. Or 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.

  The fine particles (A) can be obtained by dispersing a solvent solution of the resin (a1) having the reactive functional group and, if necessary, the curing agent (a2) in water and removing the solvent. Alternatively, the resin (a1) and, if necessary, the curing agent (a2) are melt-kneaded, cooled and pulverized.

  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 resin (a1) containing a reactive functional group and, if necessary, the curing agent (a2) include aromatic hydrocarbon solvents, aliphatic or alicyclic types. Hydrocarbon solvents, halogen solvents, ester or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and two or more of these The mixed solvent 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 a reactive functional group (alcoholic hydroxyl group, phenolic hydroxyl group, amino group, carboxylic acid group, phosphoric acid group, thiol group, etc.), for example, acrylic resin (a1-1) , Polyester resin (a1-2), polyurethane resin (a1-3), epoxy resin (a1-4) and the like.
Among these, an acrylic resin (a1-1) is preferable.
The active hydrogen equivalent of the above (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).
The above (a1-1) is produced by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization and the like, and the weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 50, 000, more preferably 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.
As the above (a1-1-2), hydroxyalkyl (2 to 4 carbon atoms) (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) An acrylate etc. are mentioned. 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 the above (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, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, polyhexamethylene carbonate diol, etc. Can be mentioned.

  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; 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 multiple steps under 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, the epoxy resin (a1-4) is preferably 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.

As blocking agents, lactams (ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), phenols (phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, etc.), oximes (methyl ethyl ketone oxime, 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), uretdiones (isophorone diisocyanate dimer, hexamethylene diisocyanate dimer, etc.), amides (acetanilide) Acid amides), 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 ratio of the resin (a1) having a reactive functional group and the curing agent (a2) is from 1/1 to less than 2/1, preferably 1 as the molar ratio of the functional group of (a1) to the isocyanate group of (a2). 2/1 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 be added in the aqueous medium, in the fine particles (A), or in the solution of (A).

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.

  In addition, in the range which does not inhibit the effect of the present invention, other known emulsifiers or surfactants (nonionic emulsifiers and surfactants, various reactive emulsifiers and surfactants) and the like are used together with (B) as necessary. be able to. 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 weathering 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; Benzotriazole ultraviolet absorbers such as (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole; 2-ethylhexyl-2-cyano- Cyanoacrylate ultraviolet absorbers such as 3,3′-diphenylacrylate; 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 ethylene-acryl copolymer and 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, 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 the above (B), the resin (a1) and, if necessary, the curing agent (a2) are dissolved in the organic solvent described above and dispersed in a reaction vessel using a homomixer or the like. If necessary, the pressure is reduced to 0.1 to 15 Torr while heating to a maximum of 100 ° C., and only the water-miscible solvent and the organic solvent are removed so that the water remains, and the volume average particle size is 0.5 μm. Method of dispersing fine particles (A) having a size of ˜50 μm in water];
(2) Grinding particle dispersion method [resin (a1), and if necessary, (a2) is melt-kneaded, cooled and pulverized to obtain fine particles (A) having a volume average particle size of 0.5 to 50 μm (B) 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 resin aqueous 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 surfactant (B) exhibits good surface activity and dispersion stability. At the same time, when (B) is a reactive surfactant (B0), the dispersion is applied and then baked to cause (B0) to chemically bond with the dispersion and to be incorporated into the film, which is excellent. Show 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, and this is 100 ° C. or more and 200 ° C. or less, preferably 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% by weight.

Production Example 1
Synthesis of Surfactant (B-1) In a reaction vessel equipped with a stirrer, dropping funnel, nitrogen gas inlet tube, thermometer, reflux condenser, 53 parts of 4-α-cumylphenol and Lewis acid catalyst (Mizusawa Chemical Industry Co., Ltd.) Made by Galleon Earth), and the system was replaced with nitrogen gas under 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 (MW900) (B0-1) in which 7 mol of styrene was added to 1 mol of 4-α-cumylphenol. (B0-1) added with EO [(EO content 45%); MW1700] 34.2 parts, polyethylene glycol (MW4000) 80.2 parts, hexamethylene diisocyanate (hereinafter abbreviated as HDI) 3.7 parts Reaction at 80 ° C. for 3 hours, MW 3,600 of polyoxyethylene chain average in hydrophilic part, oxyethylene unit content 74 wt%, MW 18,000, hydrophobic part 9 aromatic rings, hydrocarbon group carbon number 62, SP 115 parts of surfactant (B-1) having a value of 11.2 and having hydrophobic parts at both ends were obtained. Surfactant (B-1) has a triblock structure of hydrophobic part-hydrophilic part-hydrophobic part.

Production Example 2
Synthesis of surfactant (B-2) EO added to the above (B0-1) [(EO content 45%); MW1700] 36.4 parts, BPE-20 (bisphenol A EO2 mol adduct: Sanyo Kasei Kogyo Co., Ltd.) 10.2 parts, polyethylene glycol (MW8000) 79.7 parts, and HDI 3.2 parts were reacted at 80 ° C. for 3 hours, the hydrophilic part polyoxyethylene chain average MW 6,400, oxyethylene unit content 76 110% by weight, MW 28,000, hydrophobic part 9 aromatic ring, hydrocarbon group carbon number 62, SP value 11.2, surfactant (B-2) 110 parts having a hydrophobic part at both ends were obtained. . The surfactant (B-2) has a multi-block structure of hydrophobic part-hydrophilic part-hydrophobic part-hydrophilic part-hydrophobic part.

Production Example 3
Synthesis of surfactant (B-3): (B0-1) added with EO [(EO content 45%); MW1700] 34.5 parts, polyethylene glycol (MW4000) 75.7 parts, dimethylolpropion 5.5 parts of acid and 3.4 parts of HDI were reacted at 80 ° C. for 3 hours, MW 3,300 of polyoxyethylene chain average in hydrophilic part, oxyethylene unit content 75% by weight, MW 21,000, number of aromatic rings in hydrophobic part 9, 110 parts of a reactive surfactant (B-3) having a hydrocarbon group having 62 carbon atoms and an SP value of 11.2 having a hydrophobic part and a carboxylic acid as a reactive group at both ends were obtained. The surfactant (B-3) has a triblock structure of hydrophobic part-hydrophilic part-hydrophobic part.

Production Example 4
Synthesis of Surfactant (B-4) Dodecanol with EO added ((EO content 80%); MW845) 16.2 parts, polyethylene glycol (MW 6,000) 82.4 parts and HDI 3.7 parts 80 It is allowed to react at 0 ° C. for 3 hours until the NCO content becomes 0%, the polyoxyethylene chain average MW 5,500 in the hydrophilic part, the oxyethylene unit content 88% by weight, MW 19,000, the number of aromatic rings in the hydrophobic part 0, carbonization 110 parts of a surfactant (B-4) having a hydrogen group of 62 carbon atoms and an SP value of 9.1 and having a hydrophobic part at both ends were obtained. Surfactant (B-4) has a triblock structure of hydrophobic part-hydrophilic part-hydrophobic part.

Production Example 5
Synthesis of surfactant (B-5) In a reaction vessel equipped with a stirrer, dropping funnel, nitrogen gas inlet tube, thermometer, reflux condenser, 53 parts of 4-α-cumylphenol and Lewis acid catalyst (Mizusawa Chemical Co., Ltd.) Made by Galleon Earth), and the system was replaced with nitrogen gas under stirring, and the temperature was raised to 90 ° C. At the same temperature, 261 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 290 parts (MW 1500) (B0-5) obtained by adding 12 mol of styrene to 1 mol of 4-α-cumylphenol. (B0-5) added with EO [(EO content 40%); MW2500] 46.2 parts, polyethylene glycol (MW6000) 100.2 parts, HDI 4.7 parts were reacted at 80 ° C. for 3 hours to make hydrophilic Part of polyoxyethylene chain average MW 4,700, oxyethylene unit content 76% by weight, MW 23,000, hydrophobic part aromatic ring number 14, hydrocarbon group carbon number 102, SP value 11.2, at one end 138 parts of surfactant (B-5) which has a hydrophobic part was obtained. Surfactant (B-5) has a diblock structure of hydrophobic part-hydrophilic part.

Production Example 6
Synthesis of surfactant (B-6) The above (B0-1) with EO added (EO content 45%; MW 1800) 22.1 parts, polyethylene glycol (MW 6,000) 73.7 parts, HDI 4.1 Part, methyl ethyl ketone oxime (hereinafter abbreviated as MEK oxime) 0.4 part was reacted at 80 ° C. for 3 hours, and the hydrophilic part polyoxyethylene chain average MW 5,600, oxyethylene unit content 87 wt%, MW 21,000, hydrophobic 138 parts of a surfactant (B-6) having 9 parts of aromatic ring, 62 carbon atoms of hydrocarbon group and SP value of 11.2 and having a hydrophobic part only at one end was obtained. Surfactant (B-6) has a diblock structure of hydrophobic part-hydrophilic part.

Production Example 7
Preparation of Acrylic Hydroxy Functional Resin (Acrylic Resin 1) 250 parts of xylene were placed in a reactor and heated to 100 ° C., then a mixture in the proportion 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 are removed by distillation under reduced pressure, and then vacuum drying is performed to obtain an acrylic hydroxy functional resin (acrylic resin 1, SP value 10.6) having a hydroxyl group equivalent of 420 and a number average molecular weight of 12,000. It was.

Production Example 8
Preparation of Acrylic Epoxy Functional Resin (Acrylic Resin 2) 250 parts of xylene were placed in a reactor and heated to 100 ° C., then a mixture in the proportion 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) Glycidyl methacrylate 33 parts (5) Peroxy D (manufactured by Nippon Oil & Fats, peroxide) 1 part After completion of the reaction, vacuum distillation The organic solvent and the residual monomer were removed by the following step, and then the resultant was dried under vacuum to obtain an acrylic glycidyl functional resin (acrylic resin 2, SP value 10.9) having an epoxy group equivalent of 420 and a number average molecular weight of 12,000. .

Production Example 9
Preparation of polyester resin (Polyester resin 1) 200 parts of neopentyl glycol, 93 parts of ethylene glycol and 355 parts of terephthalic acid are charged into a reactor, and the reaction is continued for 2 hours while heating to 230 ° C and distilling off the water produced. It was. 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, SP value 11.4) having a value of 16.5 mgKOH / g and a hydroxyl group equivalent of 926 was obtained.

Preparation of dispersions 1 to 7 Surfactant (B-1 to B-6) obtained above and polystyrene sulfonate soda (B-7: 30 wt% aqueous solution, MW14) which is a surfactant having an anionic group 500, SP value 13.8) 3.0 parts of each were dispersed in 100 parts of water to obtain dispersions 1-7.

Reference 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 4.4 μm. Moreover, the difference in the compatibility parameter between the acrylic resin 1 and the hydrophobic part of the surfactant (B-1) was 0.6.

Reference example 2
In a beaker, 93 parts of polyester resin 1, 7 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijoule), and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 2. 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, [Sannopco Co., Ltd.] 3.0 parts were added to obtain the desired water-dispersed slurry paint having a volume average particle diameter of 4.4 μm of dispersed particles. Moreover, the difference between the compatibility parameters of the polyester resin 1 and the surfactant (B-2) was 0.2.

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 3. 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 3.9 μm. Further, the difference between the compatibility parameters of the acrylic resin 1 and the surfactant (B-3) was 0.6.

Reference example 3
In a beaker, 59 parts of acrylic resin 2, 55 parts of dodecanedicarboxylic acid, and 100 parts of tetrahydrofuran are mixed and added to 100 parts of dispersion 3, and then Ultradisperser (manufactured by Yamato Kagaku) is used. Then, mixing was performed at a rotation speed of 9,000 rpm for 1 minute, and the volume average particle diameter was set 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 4.2 μm. The difference between the compatibility parameters of the acrylic resin 2 and the surfactant (B-3) was 0.3.

Comparative Example 1
In a beaker, 59 parts of acrylic resin 1, 41 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 4. 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 6 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 4.8 μm. Moreover, the difference in the compatibility parameter between the acrylic resin 1 and the surfactant (B-4) was 1.5.

Comparative Example 2
In a beaker, 93 parts of acrylic resin 2, 7 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijoule) and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 5. 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co., Ltd.] 3.0 parts was added, and the volume average particle diameter of the dispersed particles was 4.64 μm. Moreover, the difference in the compatibility parameter between the acrylic resin 2 and the surfactant (B-5) was 1.2.

Comparative Example 3
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 4. 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts were added, and the volume average particle diameter of the dispersed particles was 4.4 μm. Moreover, the difference in the compatibility parameter between the polyester resin 1 and the surfactant (B-4) was 3.3.

Comparative Example 4
In a beaker, 93 parts of acrylic resin 1, 7 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijoule) and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 6 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts were added, and the volume average particle diameter of the dispersed particles was 4.5 μm. The difference in compatibility parameter between the acrylic resin 1 and the surfactant (B-6) was 3.3.

Comparative Example 5
In a beaker, 59 parts of acrylic resin 1, 41 parts of MEK oxime-blocked HDI trimer (Asahi Kasei, Sumijour), and 100 parts of tetrahydrofuran were mixed and added to 100 parts of dispersion 7. 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 6 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], 0.1 part of light-resistant stabilizer [“DIC-TBS”, manufactured by Dainippon Ink & Chemicals, Inc.], rheology modifier [“SN thickener-603”, Sannopco Co.] 3.0 parts was added to obtain a water-dispersed slurry paint. The volume average particle diameter of the dispersed particles was 3.9 μm. Moreover, the difference in the compatibility parameter between the acrylic resin 1 and the surfactant (B-7) was 3.2.

  Each water-dispersed slurry paint obtained by the above method was evaluated by the following test method. The results are shown in Table 1.

<Measurement of storage stability>: Based on JISK-5400-9-2, the water-dispersed slurry paint was allowed to stand at 35 ° C. for 1 week, and the state was evaluated. The evaluation criteria are as follows.
○: No abnormality (resin particles are uniformly dispersed)
Δ: Precipitation (soft; resin particles settle, and the sediment can be redispersed by simple operation)
X: Precipitation (hard; resin particles are precipitated, and the precipitate cannot be redispersed even when vigorously stirred)

(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)
<Evaluation of water resistance>: The coating film obtained above was immersed in water at 80 ° C. for 3 hours, the film after water immersion was visually observed, and the whitening state of the film surface was evaluated in three stages as follows.
○: No change is observed in the coating film.
Δ: A slight change 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 in vehicles [automobiles (body, bumpers, wipers, wheels, sunroofs, door handles, roof racks, crane exteriors, forklift exteriors, etc.), motorcycles (brake levers, baskets, etc.), railways (Shinkansen drainage). Equipment, rail joints, bolts, subway spring washers, etc.)]; civil engineering and building materials [exteriors (fences, gates, balconies, handrails, storages, terraces, curtain walls, etc.), structures (prefabricated steel frames, shutters, interior / exterior panels, Doors, etc.), others (rain gutter brackets, tiles, etc.); road materials [guard fences (guard rails, guard pipes, guard fences, bridge railings, net fences, etc.), road signs, poles (for signs, for curve mirrors] , Signal, advertising, etc.), tunnel interior panels, etc.]; electrical / communication equipment [household appliances [electronics , Pot, air conditioner (indoor unit parts and outdoor unit exterior, etc.), dehumidifier, refrigerator, washing machine, bath pot, dryer, freezer showcase, range hood, system kitchen, etc.], heavy electrical equipment (distribution panel, Switchboards, motors, generators, electrical components, etc.), others (bulbs, antennas, mercury lamps, telephones, lighting fixtures, vending machine exteriors, etc.)]; water and gas materials (steel pipes, gas water heaters, solar water heaters, etc.) Panel tanks, etc.); metal products [containers (cylinders, drums, containers, brewing tanks, etc.), steel furniture (desks, tabletops, lockers, etc.), etc. (interior parts, etc.)]; Safety equipment (fire extinguishers, fire extinguishing equipment, etc.); Agricultural materials (tractors, farming tools, nursery equipment, etc.); Ships (screws, radar, outboard motors, etc.); Sports and leisure equipment (skis) , Helmets, etc.), it can be widely used for coating applications such as.

Claims (6)

Volume consisting of resin (a1) having at least one reactive functional group selected from the group consisting of alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxylic acid groups, phosphoric acid groups and thiol groups in an aqueous medium. A water-dispersed slurry paint comprising: fine particles (A) having an average particle size of 0.5 μm or more and 50 μm or less, and a surfactant (B) having the following structure:
At least two hydrophobic units (U) having a hydrocarbon group having 6 to 100 carbon atoms having 1 to 12 aromatic rings as repeating units, and at least one hydrophilic unit (W) having an oxyethylene chain as repeating units Surfactant (B) having a repeating structure and both ends being a hydrophobic part (U): However, the compatibility parameter of the resin (a1) and the phase of the hydrophobic part (U) of the surfactant (B) A reactive interface having a solubility parameter difference of 0 to 1 and the surfactant (B) having at least one group selected from the group consisting of a carboxyl group, an amino group, an isocyanate group, a blocked isocyanate group and an epoxy group It is an activator.

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 surfactant (B) has a triblock structure of hydrophobic part (U) -hydrophilic part (W) -hydrophobic part (U). The weight average molecular weight of the oxyethylene chain of the surfactant (B) is 1,000 to 4,000, and the weight average molecular weight of the surfactant (B) is 1,500 to 30,000. The water-dispersed slurry paint according to any one of 1 to 3 . The water-dispersed slurry paint according to any one of claims 1 to 4, wherein the fine particles (A) are obtained by dispersing a solvent solution of the resin (a1) having a reactive functional group in water and removing the solvent. . The coating film obtained by apply | coating and baking the water-dispersed slurry coating material in any one of Claims 1-5 .