JP2002060455A - Two-liquid type aqueous resin composition and coating agent comprising the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-liquid type aqueous resin composition excellent in coating performance usable for a top coat, or the like, of an urethane- waterproofing material for a building and a coating agent comprising this composition. SOLUTION: In an aqueous composition containing main agent (A), (B) and a curing agent (C), an equivalent ratio of OH of the main agents to NCO of the curing agent is 1:3 to 2:1. The composition comprises: the main agent (A) being an aqueous dispersant of an acryl-urethane copolymer containing a hydroxyl group, which is obtained by chain elongation reaction of (a) a polyisocyanate compound, (b) a high molecular weight polyol, (c) a compound having an anionic hydrophilic group and an active hydrogen and (d) a neutralized substance of a prepolymer having an isocyanate group at the end obtained from a chain- elongating agent, using (e) an aqueous polyamine, or the like, and blocking the isocyanate group with an amine compound having a hydroxyl group; the main agent (B) being an aqueous emulsion of an acryl resin containing a hydroxyl group; and the curing agent (C) being a hydrophilic polyisocyanate compound, and a coating agent comprises this composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a two-part aqueous resin composition and a coating agent containing the composition. More specifically, the present invention relates to hydroxyl-containing acrylic-
A two-part aqueous resin composition obtained by blending a main agent comprising an aqueous dispersion of a urethane copolymer aqueous dispersion and an aqueous emulsion of a hydroxyl group-containing acrylic resin, and a curing agent comprising a hydrophilic polyisocyanate compound, and a composition comprising the two-part aqueous resin composition A two-pack aqueous resin composition that is useful for waterproof coatings in the construction field where severe conditions such as weather resistance and water resistance are required for various base materials such as wood, metal, plastic, and elastomer. And a coating composition containing the composition.

[0002]

2. Description of the Related Art Conventionally, organic solvent-based resins have been mainly used in the field of various adhesives, coatings such as paints and printing inks. It is being replaced by water-based resins for reasons such as environmental improvement. As an aqueous coating composition for such applications, an acrylic copolymer aqueous dispersion is inexpensive, and has excellent weather resistance, light resistance, and toughness. Is used in a wide range of fields. In recent years, with the upgrading of quality, changes in coating base materials, use for new applications, etc., demands for water-based coating compositions have become highly functional, for example, exterior walls, roofs,
In the field of cement and concrete coating for buildings, etc.,
Durability under more severe conditions is required. However, it is difficult to achieve both hardness and softness with acrylic resin alone.Soft resins generally have poor water resistance and alkali resistance, and hard resins have poor film-forming properties and crack resistance. You need quality. Water-based polyurethane paints are mainly used as coating agents for woodwork products and flooring materials because of their excellent elasticity, gloss and abrasion resistance. However, this coating film is required to be further improved in water resistance, durability, and solvent resistance. By blending, compounding, or copolymerizing the acrylic resin aqueous emulsion and the aqueous urethane resin in order to improve such drawbacks, the durability of both the advantageous properties of the urethane resin and the acrylic resin is improved. Various excellent aqueous resins have been developed. However, in the method by blending, satisfactory performance has not yet been obtained, such as turbidity of a coating film due to poor compatibility, and reduction in alkali resistance and water resistance when the amount of urethane increases.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an adhesive, water resistance, weather resistance, light resistance, and low temperature which can be used as a top coat of a super-fast curing type urethane waterproof material in waterproof coating of a building. An object of the present invention is to provide a two-part aqueous resin composition having excellent low-temperature characteristics such as flexibility and a coating agent containing the composition.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, (A) neutralized isocyanate group-terminated prepolymer obtained from a specific component was dissolved in water. Aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer in which terminal isocyanate groups are blocked, obtained by reacting a primary or secondary amine compound having a hydroxyl group after or simultaneously with the chain extension. And (B) a two-component aqueous resin composition obtained by blending a main agent composed of an aqueous emulsion of a hydroxyl group-containing acrylic resin and a curing agent composed of (C) a hydrophilic polyisocyanate compound at a specific ratio, It was found that a coating film having excellent adhesion to urethane-based waterproofing material, water resistance, weather resistance, stain resistance, and smoothness of the coated surface was formed, and the present invention was completed based on this finding. Led was. That is, the present invention
(1) In a two-pack type aqueous resin composition containing the main agent (A), the main agent (B) and the curing agent (C), the equivalent ratio of the hydroxyl group (OH) of the main agent to the isocyanate group (NCO) of the curing agent. OH / NCO is 1: 3 to 2: 1 and the main agent (A)
However, (a) an organic polyisocyanate compound, (b) a glass transition temperature of -50 to 100 ° C, and a hydroxyl value of 5
5 to 6 mg of acrylic polyol of 200 mgKOH / g
0% by weight of a high molecular weight polyol, (c) a compound having an anionic hydrophilic group and two or more active hydrogens, and (d) a neutralized isocyanate group-terminated prepolymer obtained from a chain extender (d) Is subjected to a chain extension reaction in water using at least one selected from the group consisting of (e) a water-soluble polyamine, hydrazine and derivatives thereof, or simultaneously with the chain extension reaction, (f) a hydroxyl group-containing A hydroxyl group-containing acryl-urethane copolymer aqueous dispersion obtained by blocking a terminal isocyanate group using at least one selected from the group consisting of primary and secondary amine compounds, wherein the main component (B) is Aqueous emulsion of hydroxyl group-containing acrylic resin, curing agent
(C) is a hydrophilic polyisocyanate compound, a two-part aqueous resin composition, (2) the main component (B),
(g) 1 carbon atom having at least one hydroxyl group
And / or a methacrylate having an alkyl group of from 12 to 12
(h) 1 carbon atom having at least one hydroxyl group
The two-part aqueous resin composition according to claim 1, which is an aqueous emulsion of a hydroxyl group-containing acrylic resin obtained by polymerizing an acrylate having an alkyl group of from 8 to 8, (3).
(a) the two-part aqueous resin composition according to (1) or (2), wherein the organic polyisocyanate compound is at least one selected from aliphatic diisocyanate compounds and alicyclic diisocyanate compounds; ), (F)
4. The two-part aqueous solution according to claim 1, wherein the content of the hydroxyl group derived from the component is 0.1 to 5% by weight based on the weight of the hydroxyl group-containing acrylic-urethane copolymer. The resin composition, (5) the first, second, third, or third item, wherein the content of the hydroxyl group in the main agent (B) is 0.1 to 5% by weight based on the weight of the hydroxyl group-containing acrylic resin. The two-part aqueous resin composition according to item 4, and
(6) A coating agent comprising the two-package aqueous resin composition according to (1), (2), (3), (4) or (5). is there.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The two-part aqueous resin composition of the present invention comprises (A) an aqueous dispersion of a hydroxyl group-containing acrylic-urethane copolymer and (B) an aqueous emulsion of a hydroxyl group-containing acrylic resin as main components, (C) A composition using a hydrophilic polyisocyanate compound as a curing agent. (A) hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion used in the present invention, (a) organic polyisocyanate compound,
(b) a high molecular weight polyol containing 5 to 60% by weight of an acrylic polyol having a glass transition temperature of -50 to 100 ° C and a hydroxyl value of 5 to 200 mgKOH / g;
In (c) a compound having an anionic hydrophilic group and two or more active hydrogens and (d) an isocyanate group-terminated prepolymer obtained from a chain extender (urethane prepolymer having an isocyanate group at a terminal) After elongation reaction of the hydrate in water using at least one selected from the group consisting of (e) water-soluble polyamine, hydrazine and derivatives thereof, or simultaneously with the chain elongation reaction,
(f) Aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer obtained by blocking a terminal isocyanate group using at least one selected from the group consisting of primary and secondary amine compounds having a hydroxyl group It is. The (a) organic polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexane Alicyclic diisocyanate compounds such as xylmethane diisocyanate and norbornane diisocyanate; and aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate and xylylene diisocyanate. One of these organic polyisocyanate compounds can be used alone, or two or more can be used in combination. Among them, the aliphatic diisocyanate compound and the alicyclic diisocyanate compound can be suitably used because a non-yellowing coating film can be obtained, and isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and Hexamethylene diisocyanate can be particularly preferably used.

The high molecular weight polyol (b) used in the present invention contains 5 to 60% by weight of an acrylic polyol having a glass transition temperature of -50 to 100 ° C. and a hydroxyl value of 5 to 200 mgKOH / g. The acrylic polyol is a homopolymer or a copolymer obtained from an acrylic monomer having one ethylenically unsaturated group and a hydroxyl group by a bulk polymerization method, a solution polymerization method, or the like. Examples of the acrylic monomer having one ethylenically unsaturated group and a hydroxyl group include, for example, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate,
Hydroxyhexyl acrylate, 3-chloro-2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, 5.6
Examples include dihydroxyhexyl methacrylate. One of these acrylic monomers can be used alone, or two or more of them can be used in combination. Examples of monomers copolymerizable with an acrylic monomer having one ethylenically unsaturated group and a hydroxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate , Isopropyl (meth) acrylate, n-butyl
(Meth) acrylate, isobutyl (meth) acrylate,
sec-butyl (meth) acrylate, tert-butyl (meth)
Acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2 -Chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, benzyl (meth)
Acrylate, hexafluoroisopropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2
-N-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-nitro-2-methylpropyl (meth) acrylate, furfuryl (meth) acrylate, cyclopentyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrapyranyl (meth) acrylate, benzyl (meth) acrylate, cinnamyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenylethyl (Meth) acrylate, phenyl (meth) acrylate, acrylic monomers such as (meth) acrylic acid,
Acrylonitrile, vinyl acetate, vinylpyridine, vinylpyrrolidone, methylcrotonate, maleic anhydride,
Examples include ethylenic monomers such as styrene and α-methylstyrene. Incidentally, the above (meth) acrylate means acrylate and methacrylate,
(Meth) acrylic acid means acrylic acid and methacrylic acid. One of these copolymerizable monomers can be used alone, or two or more can be used in combination.

In the present invention, the acrylic polyol contained in the high molecular weight polyol (b) has a glass transition temperature of -50 to 100 ° C, more preferably -40 to 70 ° C, and a hydroxyl value of 5 to 200 mgKOH / g. , More preferably 30 to 70 mgKOH / g. If the glass transition temperature is lower than -50 ° C, the water resistance and alkali resistance of the coating film may be insufficient. Glass transition temperature is 100 ℃
If it exceeds 300, the film forming property and the crack resistance may be insufficient. Further, when the hydroxyl value is less than 5 mgKOH / g, the number of bonding points between the acrylic resin and the urethane resin decreases, and the performance as a copolymer may not be sufficiently exhibited. Hydroxyl value of acrylic polyol is 200mg
If KOH / g is exceeded, gelation due to an increase in crosslink density proceeds during the preparation of the isocyanate group-terminated prepolymer,
Manufacturing may be difficult. The weight average molecular weight of the acrylic polyol used in the present invention is 1,000 to 500,
8,000, preferably 8,000 to 30,000
Is more preferable. The high molecular weight polyol (b) used in the present invention is obtained by converting the above acrylic polyol to 5 to 60.
%, More preferably 10 to 30% by weight. When the content of the acrylic polyol is less than 5% by weight, the acrylic resin may not be able to exhibit advantageous properties such as light resistance and weather resistance, and (B) an aqueous emulsion of a hydroxyl group-containing acrylic resin. There is a possibility that the compatibility with the polymer may decrease. When the content of the acrylic polyol exceeds 60% by weight, mechanical resistance due to the urethane resin,
There is a possibility that the development of advantageous properties such as elasticity may be insufficient.

[0008] The high molecular weight polyol (b) used in the present invention contains other polyol components in addition to the acrylic polyol. Other polyols are not particularly limited, but polyester polyols, polycarbonate polyols, and polyether polyols can be suitably used. There is no particular limitation on the polyester polyol, for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol,
Polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) Adipate) diol, polycondensates of 1,6-hexanediol and dimer acid, and the like. The polycarbonate polyol is not particularly limited. For example, polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexanedimethylene carbonate) diol, poly (hexamethylene-1,4-cyclohexyl) (Sandimethylene carbonate) diol and the like. The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers and block copolymers of ethylene oxide and propylene oxide, and ethylene oxide and butylene oxide. Further, a polyether polyester polyol having an ether bond and an ester bond can be used.

Further, a rosin-containing polyol can be used as another polyol component. The rosin-containing polyol is a reaction product composed of one molecule of a diepoxy compound and two molecules of a rosin. There is no particular limitation on the rosins used, for example, gum rosin, wood rosin, natural rosin such as tall oil rosin, purified rosin, disproportionated rosin, refined disproportionated rosin, processed rosin such as hydrogenated rosin, and the like. Mixtures and the like can be mentioned. As the diepoxy compound, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
Aliphatic diglycidyl ethers such as dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; Bis (4-hydroxyphenyl) propane diglycidyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl)
Aromatic and alicyclic diglycidyl ethers such as propane diglycidyl ether, cycloaliphatic such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and vinylcyclohexane dioxide, cyclic oxiranes, etc. Can be mentioned.
One of the above-mentioned other polyols can be used alone, or two or more can be used in combination. In the present invention, it is more preferable that the high molecular weight polyol (b) contains a dimer diol as a modifying polyol in addition to the above-mentioned polyol component. The dimer diol is a polyol containing a diol obtained by reducing dimer acid as a main component. Dimer acid is
Oleic acid, linoleic acid, linoleic acid and other unsaturated fatty acids having mainly 18 carbon atoms, drying oil fatty acids, semi-dry oil fatty acids, or lower monoalkyl esters of these fatty acids, optionally using a catalyst, It is a compound obtained by Alder-type bimolecular polymerization. Although various types of dimer acids are commercially available, typical examples are 0 to 5% by weight of a monocarboxylic acid having 18 carbon atoms, 70 to 98% by weight of a dimer acid having 36 carbon atoms, and 54 to 54% by weight. Of tricarboxylic acids of 0 to 30% by weight. (b) In the high molecular weight polyol, the content of the dimer diol is preferably from 1 to 30% by weight, and more preferably from 5 to 15% by weight. When the content of the dimer diol is 1% by weight or more, the compatibility with the plasticizer contained in the urethane-based waterproofing material is improved,
Although it shows higher adhesion, if it exceeds 30% by weight, the physical properties derived from the urethane resin may be reduced.

There is no particular limitation on the compound (c) containing an anionic hydrophilic group and at least two active hydrogens used in the present invention, but the anionic hydrophilic group is a carboxyl group,
A compound in which active hydrogen is hydrogen of a hydroxyl group can be suitably used. Such compounds include, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and the like. Further, as such a carboxyl group-containing diol, a diol component obtained by mixing a diol having a carboxyl group and a diol having no carboxyl group as required, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and an alicyclic dicarboxylic acid. A polyester polyol having a pendant carboxyl group obtained from a dicarboxylic acid such as the above can also be used. One of these compounds having an anionic hydrophilic group and two or more active hydrogens can be used alone, or two or more can be used in combination. In the present invention, a neutralized isocyanate group-terminated prepolymer refers to a trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyldiethanolamine, N, N (C) using an amine such as dimethylmonoethanolamine, N, N-diethylmonoethanolamine, and triethanolamine, potassium hydroxide, sodium hydroxide, and ammonia, and (c) an anionic hydrophilic group and two or more activities. It is obtained by neutralizing an anionic hydrophilic group of a compound having hydrogen. In the present invention, (c) the compound having an anionic hydrophilic group and two or more active hydrogens preferably has a carboxyl group as the anionic hydrophilic group, and the content of the carboxyl group is a hydroxyl group-containing acryl-urethane. It is preferably 0.3 to 2.5% by weight of the copolymer,
More preferably, it is 0.5 to 1.5% by weight. When the content of the carboxyl group is less than 0.3% by weight, the emulsification of the hydroxyl group-containing acryl-urethane copolymer may be difficult, or the emulsion stability may be insufficient. If the carboxyl group content exceeds 2.5% by weight, the water resistance of the coating film may be reduced.

In the present invention, (d) a chain extender can be used, if necessary, when preparing the isocyanate group-terminated prepolymer. There is no particular limitation on the chain extender used. For example, low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and sorbitol, ethylenediamine, propylenediamine Hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, low-molecular-weight polyamines such as diethylenetriamine and triethylenetetramine. One of these chain extenders can be used alone, or two or more can be used in combination. In the present invention, the above component (a),
Using the component (b), the component (c) and, if necessary, the component (d),
An isocyanate group terminated prepolymer is prepared. The isocyanate group-terminated prepolymer can be prepared, for example, by a conventionally known one-shot method (one-stage method) or a multi-stage isocyanate polyaddition reaction method at a reaction temperature of about 40 to 150 ° C. At this time, if necessary, dibutyltin dilaurate, stannas octoate,
A reaction catalyst such as dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine can be added. One of these reaction catalysts can be used alone, or two or more can be used in combination. Further, an organic solvent which does not react with the isocyanate group can be added at the reaction stage or after the completion of the reaction. Examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane,
Examples thereof include dimethylformamide and N-methylpyrrolidone.

In the present invention, a neutralized product of an isocyanate group-terminated prepolymer is subjected to a chain extension reaction in water using at least _one selected from the group consisting of (e) a water-soluble polyamine, hydrazine and derivatives thereof. Or
Simultaneously with the chain elongation reaction, the isocyanate group-terminated prepolymer is blocked by blocking the terminal isocyanate group with at least one selected from the group consisting of (f) primary and secondary amine compounds having a hydroxyl group. A hydroxyl group is introduced into the hydrate. Examples of the water-soluble polyamine used as the component (e) include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, and triethylenetetramine. Examples of the water-soluble amine derivative used as the component (e) include a diprimary amine and an amidoamine derived from a monocarboxylic acid, and a diprimary amine monoketimine. The hydrazine derivative used as the component (e) includes, for example, at least 2
And hydrazino groups. Among them, dihydrazide of dicarboxylic acid having 2 to 10 carbon atoms and aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms can be preferably used. Examples of the dihydrazide of a dicarboxylic acid having 2 to 10 carbon atoms include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic dihydrazide. And the like. Examples of the aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms include 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine,
1 '-(1,4-butylene) dihydrazine and the like can be mentioned.

In the present invention, among the component (f) used for blocking the terminal isocyanate group, examples of the primary amine compound having a hydroxyl group include hydroxylamine, ethanolamine, 3-amino-1-propanol, -Amino-2-hydroxymethylpropane-1,
Examples thereof include 3-diol, 2-hydroxyethylethylenediamine, and 2-hydroxyethylpropylenediamine. Examples of the secondary amine compound having a hydroxyl group include N-methylethanolamine, diethanolamine, N, N′-di-2-hydroxyethylethylenediamine, N, N′-di-2-hydroxypropylethylenediamine, N, N ′. -Di-2-hydroxypropylpropylenediamine and the like. One of these amine compounds can be used alone,
Alternatively, two or more kinds can be used in combination. Among them, ethanolamine and diethanolamine can be particularly preferably used. In the present invention, the content of the hydroxyl group derived from the component (f) of the aqueous dispersion of the hydroxyl group-containing acrylic-urethane copolymer (A) is based on the weight of the hydroxyl group-containing acrylic-urethane copolymer which is a nonvolatile component. Based on the weight, it is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. When the content of the hydroxyl group is less than 0.1% by weight, a coating film obtained from the aqueous resin composition after the two-pack preparation may have insufficient water resistance due to insufficient crosslinking density. 5% by weight hydroxyl content
If it exceeds, the liquid stability of the aqueous resin composition after the two-pack preparation is reduced, and there is a possibility that use becomes difficult. In the present invention, when an isocyanate-terminated prepolymer is prepared using an organic solvent, it is preferable to block the terminal isocyanate group and then remove the organic solvent by, for example, distillation under reduced pressure. When removing the organic solvent, surfactants, for example, higher fatty acid salts, resin salts, acidic fatty alcohols, long-chain fatty alcohol sulfates, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oil It is preferable to use a combination of an anionic surfactant such as sulfosuccinate, a nonionic surfactant such as a reaction product of ethylene oxide with a long-chain fatty alcohol or a phenol, and the like to maintain emulsifiability.

Use in the two-part aqueous resin composition of the present invention
(B) an aqueous emulsion of a hydroxyl group-containing acrylic resin comprises (g) a methacrylate having an alkyl group having 1 to 12 carbon atoms having at least one hydroxyl group and / or (h) having at least one hydroxyl group. It is preferably an aqueous emulsion of an acrylate polymer having an alkyl group having 1 to 8 carbon atoms. (B) The glass transition temperature of the hydroxyl group-containing acrylic resin is -5.
The temperature is preferably from 0 to 70 ° C, more preferably from -40 to 50 ° C. The alkyl group having 1 to 12 carbon atoms having at least one hydroxyl group of the component (g) used in the present invention may be linear or branched, and may have such an alkyl group. As the component (g), for example, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-
Examples thereof include hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, hydroxylauryl methacrylate, 3-hydroxyneopentyl methacrylate, and tetramethylolmethane methacrylate. One of these compounds can be used alone, or two or more of them can be used in combination. The alkyl group having 1 to 8 carbon atoms having at least one hydroxyl group of the component (h) used in the present invention may be linear or branched, and may have such an alkyl group. As the component (h), for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate,
Examples thereof include 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 2-hydroxyisopropyl acrylate, and tetramethylol methane acrylate. One of these compounds can be used alone, or 2
A combination of more than one species can also be used.

In the present invention, in the production of the aqueous emulsion of (B) a hydroxyl group-containing acrylic resin, in addition to the above components (g) and (h), a vinyl monomer having no hydroxyl group may be used. Can be copolymerized. There is no particular limitation on the vinyl monomer containing no hydroxyl group, and for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, lauryl methacrylate Methacrylate having a hydrocarbon group having 1 to 12 carbon atoms, such as cyclohexyl methacrylate; ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Butyl acrylate, isobutyl acrylate, tert-
C1-C8 such as butyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate Acrylate having a hydrocarbon group; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, acrylonitrile, acrylamide, methacrylamide, styrene, vinyl acetate, α
-Methylstyrene, ethylene, vinyl chloride and the like. One of these monomers can be used alone, or two or more thereof can be used in combination. In the present invention, among the above-mentioned monomers used for producing a hydroxyl group-containing acrylic resin, it is possible to impart hardness and toughness to the coating film by copolymerizing the (g) component and methacrylate having no hydroxyl group. It is possible to impart flexibility and elasticity to the coating film by copolymerizing the component (h) and the acrylate having no hydroxyl group. Further, the minimum film forming temperature of the obtained aqueous emulsion can be adjusted by a monomer other than methacrylate and acrylate having no hydroxyl group. In the present invention, there is no particular limitation on the mixing ratio of the component (g), the component (h) and the monomer having no hydroxyl group, and the required (B) performance of an aqueous emulsion of a hydroxyl group-containing acrylic resin is required. It can be appropriately selected depending on the situation.

In the present invention, the hydroxyl group content of the component (B) is preferably 0.1 to 5% by weight based on the weight of the hydroxyl group-containing acrylic resin. If the content of the hydroxyl group is less than 0.1% by weight, the coating film obtained from the two-pack type aqueous resin composition may have insufficient water resistance due to insufficient crosslinking density. When the content of the hydroxyl group exceeds 5% by weight, the liquid stability after the two-liquid preparation is reduced, and there is a possibility that use becomes difficult.
The aqueous emulsion of the hydroxyl group-containing acrylic resin (B) used in the present invention can be produced by emulsion polymerization. As the emulsifier used in the emulsion polymerization, for example,
Anionic emulsifiers such as sodium dodecylbenzene sulfate, sodium dodecylbenzenesulfonate, and alkylaryl polyether sulfate; nonionic properties such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene polyoxypropylene block copolymer Emulsifier; cationic emulsifiers such as cetyltrimethylammonium bromide and laurylpyridinium chloride; In addition, a water-soluble polymer such as polyvinyl alcohol and hydroxyethyl cellulose or a water-soluble oligomer thereof can be used in combination with an emulsifier. The total amount of these emulsifiers, water-soluble oligomers and water-soluble polymer substances is 0.5 to 1 with respect to 100 parts by weight of the monomers used for emulsion polymerization.
It is preferably 0 parts by weight. When the total amount of the emulsifier, the water-soluble oligomer and the water-soluble polymer is less than 0.5 part by weight per 100 parts by weight of the monomer, the stability of the emulsion polymerization and the stability of the obtained aqueous emulsion are reduced. There is a possibility that. If the total amount of the emulsifier, the water-soluble oligomer, and the water-soluble polymer exceeds 10 parts by weight based on 100 parts by weight of the monomer, the water resistance of the coating film may be reduced. As a radical polymerization initiator when performing emulsion polymerization,
For example, potassium persulfate, ammonium persulfate, and the like can be given. Organic peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide can also be used as needed. further,
Also used are redox initiators obtained by combining these persulfates, peroxides and the like with metal ions such as iron (II) ions, reducing agents such as sodium sulfoxylate, formaldehyde, sodium pyrosulfite and L-ascorbic acid. be able to. The concentration of the monomer in the emulsion polymerization is preferably in a range where the concentration of the hydroxyl group-containing acrylic resin, which is a nonvolatile component of the obtained aqueous emulsion, is 25 to 65% by weight. The addition of the monomer and the polymerization initiator to the reaction system can be performed by any method such as batch charging, continuous dropping, and divided addition. Reaction temperature is 40-1
The temperature is preferably 00 ° C., and the polymerization reaction is usually completed in 2 to 4 hours.

The two-part aqueous resin composition of the present invention uses (C) a hydrophilic polyisocyanate compound as a curing agent.
(C) The hydrophilic polyisocyanate compound is obtained by subjecting a polyisocyanate compound such as an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate to an addition reaction of a hydrophilic chain having active hydrogen and, in some cases, a lipophilic chain. Can be obtained by Such a hydrophilic polyisocyanate compound has good self-emulsifying dispersibility in water and a long pot life, and is effective as a curing agent for the main component composed of the components (A) and (B). In the present invention, examples of the aromatic polyisocyanate used for producing the hydrophilic polyisocyanate compound (C) include tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and hydrogenated xylylene diisocyanate. In the production of a hydrophilic polyisocyanate compound, biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, polyisocyanate compound having a trimer structure and the like, and an adduct of an aliphatic isocyanate such as trimethylolpropane Can be used. In the present invention, (C)
The hydrophilic compound used for producing the hydrophilic polyisocyanate compound is not particularly limited, but a hydrophilic compound having 5 to 50 ethylene oxide repeating units and a hydroxyl group at one terminal can be suitably used. Examples of such a hydrophilic compound include polyethylene glycol monoalkyl ether, and a monoalkyl ether of a random or block copolymer of ethylene oxide and propylene oxide. If the number of ethylene oxide repeating units is less than 5, the emulsifiability of the hydrophilic polyisocyanate compound may be insufficient. If the number of ethylene oxide repeating units exceeds 50, the crystallinity of the hydrophilic polyisocyanate compound may be increased, and the compound may be solid.

The hydrophilic polyisocyanate compound (C) used in the present invention preferably has a hydrophilic group content of 2 to 50% by weight. When the amount of the hydrophilic group is less than 2% by weight,
The effect of lowering the interfacial tension is not sufficient, and the emulsifiability of the hydrophilic polyisocyanate compound may be insufficient. If the amount of the hydrophilic group exceeds 50% by weight, the reactivity of the isocyanate group of the hydrophilic polyisocyanate compound with water may be too large. The method for producing the hydrophilic polyisocyanate compound (C) used in the present invention is not particularly limited, and isocyanate groups of the polyisocyanate compound,
It can be easily produced by reacting a terminal hydroxyl group of a hydrophilic compound. In the present invention,
(C) As the hydrophilic polyisocyanate compound, for example,
Modified adduct of hexamethylene diisocyanate [Asahi Kasei Corporation, Duranate WB40-80D], Modified isocyanurate of hexamethylene diisocyanate [Sumitomo Bayer Urethane Co., Ltd., Bihidule 310]
0], [Nippon Polyurethane Industry Co., Ltd., Aquanate 10
0, Aquanate 200]. In the two-part aqueous resin composition of the present invention,
(A) an aqueous dispersion of a hydroxyl group-containing acrylic-urethane copolymer and (B) an aqueous emulsion of a hydroxyl group-containing acrylic resin; and (C) an isocyanate group (NC) of a curing agent comprising a hydrophilic polyisocyanate compound.
The equivalent ratio OH / NCO of O) is blended so as to be 1: 3 to 2: 1. If the equivalent ratio OH / NCO is less than 1: 3, excess isocyanate groups may react with water to generate carbon dioxide gas, which may impair the appearance of the coating film. Equivalent ratio O
If the H / NCO exceeds 2: 1, the crosslinking density required to obtain sufficient coating strength is insufficient, and the water resistance may be reduced due to exposure of the hydroxyl groups. Main ingredient
The mixing ratio of (A) and the main agent (B) is not particularly limited, and can be appropriately selected according to the required performance of the two-part aqueous resin composition.

In the two-pack type aqueous resin composition of the present invention, if necessary, various surfactants such as fluorine-based and acetylene-glycol-based surfactants, and n-
Methyl pyrrolidone, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and the like can be added. The two-part aqueous resin composition of the present invention itself has excellent resin physical properties with respect to durability, weather resistance, and water resistance, but includes an aqueous oxazoline crosslinking agent, an aqueous polycarbodiimide crosslinking agent, and an aqueous epoxy resin crosslinking. An excellent water resistance can also be imparted by using a crosslinking agent having reactivity with a carboxyl group such as an agent in combination. The two-component aqueous resin composition of the present invention can be suitably used for various plastic base materials and elastomers as various coating agents such as adhesives, paints, and printing inks, and particularly, urethane-based materials for buildings. When it is a topcoat agent for waterproofing materials, it shows excellent adhesion and demands such as smoothness, water resistance, weather resistance, stain resistance, and low temperature flexibility, which are important properties for such a composition. Can be satisfied. The reason that the two-part aqueous resin composition of the present invention exhibits the above-mentioned effects is that the main component (A) is a hydroxyl group-containing acryl-urethane copolymer aqueous dispersion.
(B) good compatibility with the aqueous emulsion of the hydroxyl group-containing acrylic resin, and formation of a high crosslink density that cannot be obtained with a one-pack type aqueous resin by using (C) a hydrophilic polyisocyanate compound as a curing agent It is supposed to be.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, the properties of the coating film were evaluated by the following methods. (1) Preparation of coating film The coating film was evaluated by applying a coating agent to a 2 mm-thick urethane waterproof sheet [Daiflex Co., Ltd., SP-100] so that the film thickness would be 0.2 mm. After standing at 25 ° C. for one week, the test is performed. (2) Transparency of coating film A coating agent is applied to a glass plate, and the transparency of the coating film is visually evaluated. ；: Transparent △: slightly white ×: white (3) Appearance of coating film Cracks appearing in the coating film are visually evaluated. ；: No crack was observed. Δ: Slight cracking is observed. X: Cracks are clearly observed. (4) Adhesion In accordance with JIS K 5400 8.5.2, a checkerboard-shaped grid 1 with a gap of 1 mm was applied to the coating film using a cutter knife.
After making 00 pieces, a cellophane adhesive tape [Nichiban Co., Ltd.] was adhered, and the appearance of the coating film when rapidly peeled off at an angle of 60 ° was observed, and evaluated according to the following criteria. A: 95% or more of the coating film remains on the adherend side. ；: 80% or more and less than 95% of the coating film remain on the adherend side. Δ: 50% or more and less than 80% of the coating film remain on the adherend side. ×: Less than 50% of the coating film remains on the adherend side. (5) Warm water resistance After the coating film was immersed in water at 50 ° C. for 24 hours, JIS K
5400 According to 8.5.2.
Make 100 grids with a 1 mm gap on the coating film and glue cellophane adhesive tape [Nichiban Co., Ltd.]
The appearance of the coating film when rapidly peeled off at an angle of 60 degrees is observed and evaluated according to the following criteria. A: 95% or more of the coating film remains on the adherend side. ；: 80% or more and less than 95% of the coating film remain on the adherend side. Δ: 50% or more and less than 80% of the coating film remain on the adherend side. ×: Less than 50% of the coating film remains on the adherend side. (6) Weather resistance According to JIS K 5400 9.8.1, the coating film is irradiated with a sunshine weather meter for 500 hours, and the gloss retention of the coating film is measured and evaluated according to the following criteria. ○: Gloss retention of 80% or more △: Gloss retention of 60% to less than 80% ×: Gloss retention of less than 60% (7) Stain resistance 10 of carbon black [Mitsubishi Chemical Corporation, MA100]
A weight% aqueous dispersion is applied by spraying, dried at 80 ° C. for 2 hours, washed with water, and visually evaluated for contamination on the coating film. ；: Black color is not recognized. Δ: Slight black color is observed. X: Black is clearly observed.

Synthesis Example 1 (Hydroxy group-containing acryl-
Acrylic polyol [Dainippon Ink and Chemicals, Acridic A-808T, nonvolatile] in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube. 50% by weight, hydroxyl value about 20 mgKOH / g, glass transition temperature 97 ° C] 56 parts by weight, polyhexamethylene carbonate diol [number average molecular weight 1,000] 80 parts by weight, 1,4-butanediol 0.9 part by weight 6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone, and after uniformly mixing, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added. ° C
For 2 hours to obtain a solution of an isocyanate group-terminated prepolymer in methyl ethyl ketone having a free isocyanate group content of 1.7% by weight based on the nonvolatile content. This solution is
After cooling to 0 ° C. and neutralizing by adding 5 parts by weight of triethylamine, 350 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion, 6 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added and stirred for 0.5 hours. Further, 6.3 parts by weight of diethanolamine was added and stirred for 2 hours. Next, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in this hydroxyl group-containing acryl-urethane copolymer is 1.3% by weight, and the content of hydroxyl groups derived from diethanolamine is 1.2% by weight. . This aqueous dispersion of the copolymer is referred to as an aqueous dispersion of hydroxyl-containing acryl-urethane copolymer A. Synthesis Example 2 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion) An acrylic polyol [Dainippon Ink Chemical Industry Co., Ltd., Acrylic A-809, non-volatile] was used in the same reactor as used in Synthesis Example 1. About 50% by weight, glass transition temperature 6
1 ° C, hydroxyl value about 20 mgKOH / g] 112 parts by weight, polybutylene adipate diol [number average molecular weight 1,700] 102 parts by weight, 2,2-dimethylolbutanoic acid 7.4 parts by weight, dibutyltin dilaurate 0.001 Parts by weight and 60 parts by weight of methyl ethyl ketone, and uniformly mixed. Then, 44.6 parts by weight of isophorone diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. A solution of the terminal prepolymer in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C., neutralized by adding 5 parts by weight of triethylamine, and gradually added with 350 parts by weight of water to emulsify and disperse. To this emulsified dispersion, 12.6 parts by weight of diethanolamine was added and stirred for 2 hours.
Next, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolbutanoic acid in this hydroxyl group-containing acryl-urethane copolymer is 1.0% by weight, and the content of hydroxyl groups derived from diethanolamine is 1.8% by weight. . This copolymer aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion B. Synthesis Example 3 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion) An acrylic polyol [Dainippon Ink and Chemicals Acrylic A-811, nonvolatile] was used in the same reactor as used in Synthesis Example 1. About 50% by weight, glass transition temperature 5
8 ° C., hydroxyl value about 17 mg KOH / g] 66 parts by weight,
80 parts by weight of poly-3-methylpentane adipate [number average molecular weight 2,000], dimer diol [Toagosei
Co., Ltd., Pespol HP-1000, number average molecular weight 57
0] 23 parts by weight, 7.4 parts by weight of 2,2-dimethylolbutanoic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were mixed and uniformly mixed, and then dicyclohexylmethane diisocyanate 52.
4 parts by weight were added, and the mixture was reacted at 80 ° C. for 2 hours to obtain a solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.5% by weight based on the nonvolatile matter in methyl ethyl ketone. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, and then gradually emulsified and dispersed by adding 350 parts by weight of water. In this emulsified dispersion,
1.6 parts by weight of a 60.0% by weight aqueous solution of hydrazine hydrate was added, and the mixture was stirred for 0.5 hour.
4 parts by weight were added and stirred for 2 hours. Next, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolbutanoic acid in this hydroxyl group-containing acryl-urethane copolymer is 1.1% by weight.
And the content of hydroxyl groups derived from diethanolamine is 1.3% by weight. This copolymer aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion C. Synthesis Example 4 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion) Acrylic polyol [Dainippon Ink and Chemicals, Acridic A-811, nonvolatile] was used in the same reactor as used in Synthesis Example 1. About 50% by weight, glass transition temperature 5
8 ° C., hydroxyl value about 17 mg KOH / g] 66 parts by weight, poly-ε-caprolactone diol [number average molecular weight 2,000] 80 parts by weight, dimer diol [Toagosei Co., Ltd.]
Co., Ltd., Pespol HP-1000, number average molecular weight 57
0] 23 parts by weight, 2,2-dimethylolbutanoic acid 7.
4 parts by weight were dissolved in 30 parts by weight of methyl ethyl ketone, neutralized by adding 5.0 parts by weight of triethylamine, 0.001 part by weight of dibutyltin dilaurate and 30 parts by weight of methyl ethyl ketone were mixed and uniformly mixed. Methane diisocyanate 52.4
The mixture was reacted at 80 ° C. for 2 hours to obtain a solution of a neutralized isocyanate group-terminated prepolymer having a free isocyanate group content of 1.5% by weight based on the nonvolatile content in methyl ethyl ketone. The solution was cooled to 30 ° C.
0 parts by weight was gradually added and emulsified and dispersed. To this emulsified dispersion, 1.6 parts by weight of a 60% by weight aqueous hydrazine aqueous solution was added and stirred for 0.5 hours, and 8.4 parts by weight of diethanolamine was further added and stirred for 2 hours. Next, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolbutanoic acid in this hydroxyl group-containing acryl-urethane copolymer is 1.2.
% By weight, and the content of hydroxyl groups derived from diethanolamine is 1.3% by weight. This aqueous dispersion of the copolymer is referred to as an aqueous dispersion of hydroxyl group-containing acryl-urethane copolymer D.

Comparative Synthesis Example 1 (Aqueous Dispersion of Acrylic-Urethane Copolymer) In the same reactor as used in Synthesis Example 1, an acrylic polyol [Dainippon Ink Chemical Industry Co., Ltd., Acrylic A-809, Non-volatile content 50% by weight, hydroxyl value about 2
0 mgKOH / g, glass transition temperature 61 ° C] 112 parts by weight,
Polybutylene adipate diol [number average molecular weight 1,7
00] 85 parts by weight, 1.2 parts by weight of ethylene glycol,
6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone are charged and uniformly mixed, and then 44.6 parts by weight of isophorone diisocyanate is added. The reaction was carried out for a period of time to obtain a solution of the isocyanate group-terminated prepolymer in methyl ethyl ketone having a free isocyanate group content of 1.7% by weight based on the nonvolatile content. Add this solution to 30
After cooling to 5 ° C. and neutralizing by adding 5 parts by weight of triethylamine, 350 parts by weight of water was gradually added and emulsified and dispersed. To this emulsified dispersion, 5 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added and stirred for 2 hours. Next, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of an acrylic-urethane copolymer having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in the acrylic-urethane copolymer is 1.0% by weight. This aqueous copolymer dispersion is referred to as an aqueous acryl-urethane copolymer dispersion E. Comparative Synthesis Example 2 (Hydroxyl Group-Containing Urethane Resin Aqueous Dispersion) In the same reactor as used in Synthesis Example 1, poly-ε-
Caprolactone diol [number average molecular weight 2,000] 1
00 parts by weight, 10 parts by weight of polyethylene glycol [number average molecular weight 1,000], 6.7 parts by weight of 2,2-dimethylolpropionic acid, 2.7 parts by weight of 1,4-butanediol, 0.001 part of dibutyltin dilaurate Parts by weight and 60 parts by weight of methyl ethyl ketone, and after mixing uniformly, 52.4 parts of dicyclohexylmethane diisocyanate.
Then, the mixture was reacted at 80 ° C. for 2 hours to obtain a solution of isocyanate group-terminated prepolymer having a free isocyanate group content of 2.2% by weight based on the nonvolatile content in methyl ethyl ketone. The solution was cooled to 30 ° C., neutralized by adding 5 parts by weight of triethylamine, and gradually added with 350 parts by weight of water to emulsify and disperse. To this emulsified dispersion, 6.2 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added to form a mixture of 0.2 parts by weight.
The mixture was stirred for 5 hours, 8.4 parts by weight of diethanolamine was added, and the mixture was stirred for 2 hours. Subsequently, the solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain a hydroxyl group-containing urethane resin aqueous dispersion having a nonvolatile content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in this hydroxyl group-containing urethane resin was 1.2% by weight, and the content of hydroxyl groups derived from diethanolamine was 1.5% by weight. This urethane resin aqueous dispersion is referred to as a hydroxyl group-containing urethane resin aqueous dispersion F.

Synthesis Example 5 (Aqueous Emulsion of Hydroxyl Group-Containing Acrylic Resin) In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 265 parts by weight of water, an anionic emulsifier [p- 5 parts by weight of a 35% by weight aqueous solution of a sulfuric acid half ester sodium salt of a nonylphenol ethylene oxide 20 mol adduct and 20% by weight of a nonionic emulsifier [p-nonylphenol ethylene oxide 25 mol adduct]
20 parts by weight of the aqueous solution was charged, and the inside of the reaction vessel was replaced with nitrogen gas. In a reaction vessel, 20 parts by weight of water, 2.5 parts by weight of a 35% by weight aqueous solution of the above anionic emulsifier, 16 parts by weight of methyl methacrylate, 14 parts by weight of n-butyl acrylate, 8 parts by weight of styrene, and A monomer mixture containing 2 parts by weight of 2-hydroxyethyl was added and heated to 90C. Next, an aqueous initiator solution in which 0.25 parts by weight of potassium persulfate was dissolved in 8.5 parts by weight of water was added. Then water 1
80 parts by weight, 22.5 parts by weight of a 35% by weight aqueous solution of the above anionic emulsifier, 144 parts by weight of methyl methacrylate,
Dissolve 2.25 parts by weight of potassium persulfate in 74.5 parts by weight of a monomer mixture containing 126 parts by weight of n-butyl acrylate, 72 parts by weight of styrene, 18 parts by weight of 2-hydroxyethyl acrylate The obtained initiator aqueous solution was supplied into the reaction vessel maintained at 90 ° C. over 3.5 hours, and after the supply, polymerization was carried out at 90 ° C. for another 2 hours to obtain an aqueous emulsion of a hydroxyl group-containing acrylic resin. . The glass transition temperature of this acrylic resin was about 22 ° C. This aqueous emulsion is referred to as an aqueous emulsion A of a hydroxyl group-containing acrylic resin. Synthesis Example 6 (Aqueous Emulsion of Hydroxyl Group-Containing Acrylic Resin) In a reaction apparatus similar to that used in Synthesis Example 5, 265 parts by weight of water and an anionic emulsifier [sulfuric acid half ester of a 20 mol adduct of ethylene oxide with p-nonylphenol] were added. 5 parts by weight of a 35% by weight aqueous solution of sodium salt] and 20 parts by weight of a 20% by weight aqueous solution of a nonionic emulsifier [addition product of 25 mol of ethylene oxide of p-nonylphenol] were purged with nitrogen gas. In a reaction vessel, 20 parts by weight of water and a 35% by weight aqueous solution of the above anionic emulsifier 2.
A monomer mixture containing 5 parts by weight, 20 parts by weight of methyl methacrylate, 16 parts by weight of n-butyl acrylate, and 4 parts by weight of 2-hydroxyethyl acrylate was added, and the mixture was heated to 90 ° C. An aqueous solution of an initiator in which 0.25 part by weight of potassium persulfate was dissolved in part by weight was added. Then, 180 parts by weight of water and a 35% by weight aqueous solution of the above anionic emulsifier 2
A monomer mixture containing 2.5 parts by weight, 180 parts by weight of methyl methacrylate, 144 parts by weight of n-butyl acrylate, and 36 parts by weight of 2-hydroxyethyl acrylate;
An initiator aqueous solution obtained by dissolving 2.25 parts by weight of potassium persulfate in 4.5 parts by weight was supplied to each reaction vessel maintained at 90 ° C. over 3.5 hours, and then maintained at 90 ° C. for another 2 hours after the supply. Polymerization was carried out to obtain an aqueous emulsion of a hydroxyl group-containing acrylic resin. The glass transition temperature of this acrylic resin was about 7 ° C. This aqueous emulsion is referred to as an aqueous emulsion B of a hydroxyl group-containing acrylic resin. Comparative Synthesis Example 3 (Aqueous Emulsion of Acrylic Resin) In a reaction apparatus similar to that used in Synthesis Example 5, 265 parts by weight of water, anionic emulsifier [sodium salt of sulfuric acid half ester of 20 mol adduct of ethylene oxide with p-nonylphenol] were added. 5 parts by weight of a 35% by weight aqueous solution and 20 parts by weight of a 20% by weight aqueous solution of a nonionic emulsifier [addition product of 25 mol of ethylene oxide of p-nonylphenol] were replaced with nitrogen gas. In a reaction vessel, 20 parts by weight of water and a 35% by weight aqueous solution of the above anionic emulsifier 2.
A monomer mixture containing 5 parts by weight, 15.6 parts by weight of styrene, 12 parts by weight of methyl methacrylate, 12 parts by weight of n-butyl acrylate and 0.4 part by weight of acrylic acid was added, and 90 parts were added.
C. and an aqueous initiator solution in which 0.25 parts by weight of potassium persulfate was dissolved in 8.5 parts by weight of water. Then water 1
80 parts by weight, 22.5 parts by weight of a 35% by weight aqueous solution of the anionic emulsifier, 140.4 parts by weight of styrene, 108 parts by weight of methyl methacrylate, n-butyl acrylate 10
A monomer mixture containing 8 parts by weight and 3.6 parts by weight of acrylic acid, and an aqueous solution of an initiator obtained by dissolving 2.25 parts by weight of potassium persulfate in 74.5 parts by weight of water were each added to 9 parts over 3.5 hours.
The mixture was fed into a reaction vessel kept at 0 ° C., and after the supply, polymerization was carried out at 90 ° C. for another 2 hours to obtain an aqueous emulsion of an acrylic resin. The glass transition temperature of this acrylic resin is
It was about 36 ° C. This aqueous emulsion is referred to as an aqueous emulsion C of an acrylic resin. Monomer compositions of aqueous emulsions A and B of hydroxyl group-containing acrylic resin obtained in Synthesis Examples 5 and 6 and aqueous emulsion C of acrylic resin obtained in Comparative Synthesis Example 3, glass transition temperature and hydroxyl of acrylic resin Table 1 shows the group content.

[0024]

[Table 1]

Example 1 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 70 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion A obtained in Synthesis Example 1 and obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to a main component obtained by mixing 30 parts by weight of an aqueous emulsion A of a hydroxyl group-containing acrylic resin.
[-80D, NCO content: 13.5% by weight] 10.5 parts by weight was blended as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3.
This coating agent is brush-coated on a 2 mm-thick urethane waterproof material [DAIFLEX, SP-100] and a glass plate,
It was dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, all the coating films remained on the adherend side. In the hot water resistance test, 94% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 81%. No black color was observed in the stain resistance test. Example 2 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 50 parts by weight of hydroxyl group-containing acryl-urethane copolymer aqueous dispersion A obtained in Synthesis Example 1 and hydroxyl group-containing liquid obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the base resin obtained by mixing 50 parts by weight of an aqueous emulsion A of an acrylic resin.
[-80D, NCO content: 13.5% by weight] 9.8 parts by weight as a curing agent, and stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was brush-coated on a 2 mm-thick urethane waterproof material [Daiflex Co., Ltd., SP-100] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, all the coating films remained on the adherend side. In the warm water resistance test, 93% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 82%. No black color was observed in the stain resistance test. Example 3 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion A obtained in Synthesis Example 1 and hydroxyl group-containing obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the base resin mixed with 70 parts by weight of an aqueous emulsion A of an acrylic resin.
[-80D, NCO content 13.5% by weight] 9.1 parts by weight was blended as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was brush-coated on a 2 mm-thick urethane waterproof material [Daiflex Co., Ltd., SP-100] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, all the coating films remained on the adherend side. In the hot water resistance test, 88% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 84%. No black color was observed in the stain resistance test.

Example 4 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of the hydroxyl group-containing acryl-urethane copolymer aqueous dispersion B obtained in Synthesis Example 2 and obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the main component obtained by mixing 70 parts by weight of an aqueous emulsion A of a hydroxyl group-containing acrylic resin.
-80D, NCO content: 13.5% by weight] 10.8 parts by weight was blended as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3.
This coating agent is brush-coated on a 2 mm-thick urethane waterproof material [DAIFLEX, SP-100] and a glass plate,
It was dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, all the coating films remained on the adherend side. In the hot water resistance test, 90% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 85%. No black color was observed in the stain resistance test. Example 5 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of aqueous hydroxyl group-containing acryl-urethane copolymer dispersion B obtained in Synthesis Example 2 and hydroxyl group-containing liquid obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the base resin mixed with 70 parts by weight of an aqueous emulsion B of an acrylic resin.
[-80D, NCO content: 13.5% by weight] 19.3 parts by weight was blended as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3.
This coating agent is brush-coated on a 2 mm-thick urethane waterproof material [DAIFLEX, SP-100] and a glass plate,
It was dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, all the coating films remained on the adherend side. In the warm water resistance test, 91% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 83%. No black color was observed in the stain resistance test. Example 6 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) Hydroxyl group-containing acryl-urethane copolymer aqueous dispersion C obtained in Synthesis Example 3 (30 parts by weight) and hydroxyl group-containing obtained in Synthesis Example 6 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the base resin mixed with 70 parts by weight of an aqueous emulsion A of an acrylic resin.
[-80D, 13.5% by weight of NCO]] was added as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was brush-coated on a 2 mm-thick urethane waterproofing material [Daiflex Co., Ltd., SP-100] and a glass plate.
It was dried at 5 ° C. and 65% relative humidity for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test and the warm water resistance test, all of the coating film remained on the adherend side.
In the weather resistance test, the gloss retention was 85%. No black color was observed in the stain resistance test. Example 7 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of an aqueous dispersion of hydroxyl-containing acryl-urethane copolymer D obtained in Synthesis Example 4 and a hydroxyl group-containing liquid obtained in Synthesis Example 5 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40] was added to the base resin mixed with 70 parts by weight of an aqueous emulsion A of an acrylic resin.
[-80D, 13.5% by weight of NCO]] was added as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was brush-coated on a 2 mm-thick urethane waterproofing material [Daiflex Co., Ltd., SP-100] and a glass plate.
It was dried at 5 ° C. and 65% relative humidity for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test and the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 86%. No black color was observed in the stain resistance test.

Comparative Example 1 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) A hydrophilic polyisocyanate containing 100 parts by weight of an aqueous dispersion of the hydroxyl group-containing acryl-urethane copolymer A obtained in Synthesis Example 1 as a main component was used. Compound [Asahi Kasei Corporation, Duranate WB40-80D, NCO 13.5% by weight] 11.
5 parts by weight were blended as a curing agent, and the mixture was stirred until it became uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3.
It is. This coating agent was brush-coated on a 2 mm-thick urethane waterproof material [Daiflex Co., Ltd., SP-100] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. Regarding the appearance of the coating film, transparency was good, and no crack was observed.
In the adhesion test, all the coating films remained on the adherend side.
In the hot water resistance test, 90% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 67%. In the stain resistance test, almost all black contaminants remained. Comparative Example 2 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd.] containing 100 parts by weight of aqueous emulsion A of a hydroxyl group-containing acrylic resin obtained in Synthesis Example 5 as a main component , Duranate WB40-80D, 13.5% by weight of NCO] was blended as a curing agent, and the mixture was stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was brush-coated on a 2 mm-thick urethane waterproof material [Daiflex Co., Ltd., SP-100] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The thickness of each coating film was 0.2 mm. As the appearance of the coating film, transparency was good, but cracks were clearly observed. In the adhesion test, all the coating films remained on the adherend side. In the hot water resistance test, 75% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 84%. No black color was observed in the stain resistance test. Comparative Example 3 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of aqueous dispersion of acrylic-urethane copolymer E obtained in Comparative Synthesis Example 1 and hydroxyl group-containing acrylic resin obtained in Synthesis Example 4 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40-80D, N
5.6 parts by weight of CO13.5% by weight] as a curing agent, and stirred until uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was coated with a 2 mm-thick urethane waterproofing material [Daiflex Co., Ltd., SP-1
00] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. All coating thicknesses are 0.2m
m. Regarding the appearance of the coating film, transparency was good, and no crack was observed. In the adhesion test, 70
% Remained on the adherend side. In the hot water resistance test, 30% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 70%. In the stain resistance test, a slight black color was observed.

Comparative Example 4 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of hydroxyl group-containing urethane resin aqueous dispersion F obtained in Comparative Synthesis Example 2 and hydroxyl group-containing liquid obtained in Synthesis Example 6 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40-80D,
NCO 13.5% by weight] was mixed with 9.9 parts by weight as a curing agent, and the mixture was stirred until the mixture became uniform to prepare a coating agent. The equivalent ratio OH / NCO of the hydroxyl group in the main agent and the isocyanate group in the curing agent is 2: 3. This coating agent was coated with a 2 mm-thick urethane waterproofing material [Daiflex Co., Ltd., SP-1
00] and a glass plate, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 7 days. The coating thickness is 0.2m
m. The appearance of the coating film was slightly white, but no crack was observed. In the adhesion test, all the coating film remained on the adherend side. 42% of coating film in hot water resistance test
Remained on the adherend side. In the weather resistance test, the gloss retention was 65%. In the stain resistance test, a slight black color was observed. Comparative Example 5 (Preparation of Aqueous Resin Composition and Evaluation of Physical Properties of Coating Film) 30 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion A obtained in Synthesis Example 1 and the acrylic resin obtained in Comparative Synthesis Example 3 A hydrophilic polyisocyanate compound [Asahi Kasei Kogyo Co., Ltd., Duranate WB40-80D, NCO
13.5% by weight] 3.5 parts by weight as a curing agent were blended and stirred until uniform to prepare a coating agent. Equivalent ratio O of hydroxyl groups in the base material to isocyanate groups in the curing agent
H / NCO is 2: 3. This coating agent is coated with a 2 mm-thick urethane waterproofing material [Daiflex, SP-100].
And brush on a glass plate, temperature 25 ° C, relative humidity 65
% For 7 days. The thickness of each coating film was 0.2 mm. The appearance of the coating film was transparent, and no crack was observed. In the adhesion test, 60% of the coating film remained on the adherend side. In the hot water resistance test, 37% of the coating film remained on the adherend side. In the weather resistance test, the gloss retention was 63%. In the stain resistance test, a slight black color was observed. Table 2 shows the results of Examples 1 to 7 and Comparative Examples 1 to 5. The values in the columns of adhesion and hot water resistance are the percentage of the coating film remaining on the adherend, and the values in the weather resistance column are the gloss retention.

[0029]

[Table 2]

As can be seen from Table 2, Examples 1 to 7 using the coating compositions containing the two-package aqueous resin composition of the present invention.
, A coating film having good transparency and appearance is formed, has good adhesion to the urethane waterproofing material, and has excellent weather resistance and stain resistance. On the other hand, in Comparative Example 1, which did not contain the aqueous emulsion of the hydroxyl group-containing acrylic resin, the weather resistance was slightly inferior and the stain resistance was poor.
In Comparative Example 2, which did not contain the hydroxyl group-containing acryl-urethane copolymer aqueous dispersion, the coating film was distorted, and the warm water resistance was poor. In Comparative Example 3 in which an aqueous dispersion of an acrylic-urethane copolymer containing no hydroxyl group was used instead of the aqueous dispersion of an acrylic-urethane copolymer containing a hydroxyl group, the adhesion was slightly poor, and the hot water resistance was significantly poor. Also, the weather resistance and stain resistance are slightly inferior. In Comparative Example 4 in which a hydroxyl group-containing urethane resin aqueous dispersion containing no acrylic polyol was used instead of the hydroxyl-containing acrylic-urethane copolymer aqueous dispersion, transparency was slightly inferior, and hot water resistance was significantly inferior.
Weather resistance and stain resistance are also slightly inferior. Comparative Example 5 Using Aqueous Emulsion of Acrylic Resin Containing No Hydroxyl Group
, The adhesiveness is slightly inferior, the warm water resistance is remarkably inferior, and the weather resistance and stain resistance are also slightly inferior.

[0031]

The coating film obtained from the two-package aqueous resin composition and the coating agent of the present invention has good adhesion to a urethane-based waterproofing material,
Excellent performance as a top coat of urethane-based waterproofing materials that require strict performance requirements such as warm water resistance, weather resistance, stain resistance, and smoothness of the coated surface, and can be widely deployed as a water-based coating agent. is there.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroki Onishi 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Inside Nikka Kagaku Co., Ltd. (72) Inventor Shinichi Umetani 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Inside Nichika Chemical Co., Ltd. (72) Inventor Kenji Yoshino 1-1067-5, Kaijinmachi Nishi, Funabashi City, Chiba Prefecture (72) Inventor Makoto Takanashi, 1-1067 Nishikaijinmachi Nishi, Funabashi City, Chiba Prefecture -5 F-term in Daiflex R & D Co., Ltd. (reference) 4J034 BA08 CA04 CA11 CA12 CA14 DA01 DB01 DB04 DB05 DC50 DE02 DP18 GA15 GA33 HC03 HC09 HC12 HC17 4J038 CH121 DG061 DG191 DG271 DG291 DG321 HA156 KA03 MA08 MA10 MA13 NA14 NA12 NA12

Claims (6)

[Claims] 1. A main agent (A), a main agent (B) and a curing agent (C)
In a two-pack type aqueous resin composition containing a polymer, a hydroxyl group (OH) of a main agent and an isocyanate group (N
CO) has an equivalent ratio OH / NCO of 1: 3 to 2: 1;
The main agent (A) is (a) an organic polyisocyanate compound,
(B) a high molecular weight polyol containing 5 to 60% by weight of an acrylic polyol having a glass transition temperature of -50 to 100 ° C and a hydroxyl value of 5 to 200 mgKOH / g;
(C) a compound having an anionic hydrophilic group and two or more active hydrogens and optionally (d) a neutralized isocyanate group-terminated prepolymer obtained from a chain extender, (e) a water-soluble polyamine, After a chain elongation reaction in water using at least one selected from the group consisting of hydrazine and derivatives thereof, or simultaneously with the chain elongation reaction, (f) a primary or secondary amine compound having a hydroxyl group A hydroxyl group-containing acryl-urethane copolymer aqueous dispersion obtained by blocking a terminal isocyanate group using at least one selected from the group consisting of: a base material (B) comprising an aqueous emulsion of a hydroxyl group-containing acrylic resin; A two-part aqueous resin composition, wherein the curing agent (C) is a hydrophilic polyisocyanate compound. 2. The base material (B) comprises: (g) a methacrylate having an alkyl group having 1 to 12 carbon atoms having at least one hydroxyl group and / or (h) a methacrylate having 1 carbon atom having at least one hydroxyl group. The two-part aqueous resin composition according to claim 1, which is an aqueous emulsion of a hydroxyl group-containing acrylic resin obtained by polymerizing an acrylate having an alkyl group of from 8 to 8. 3. The method according to claim 1, wherein (a) the organic polyisocyanate compound is
The at least one member selected from an aliphatic diisocyanate compound and an alicyclic diisocyanate compound.
Or the two-part aqueous resin composition according to claim 2. 4. The main agent (A) has a hydroxyl group content derived from the component (f) of 0.1 to 5% by weight based on the weight of the hydroxyl group-containing acryl-urethane copolymer. The two-component aqueous resin composition according to claim 2 or 3. 5. The hydroxyl group content of the main agent (B) is as follows:
0.1 based on the weight of the hydroxyl group-containing acrylic resin
The two-part aqueous resin composition according to claim 1, 2 or 3, wherein the amount is from 5 to 5% by weight. 6. The first, second, third and fourth aspects of the present invention.
A coating agent comprising the two-part aqueous resin composition according to claim 5.