JPH10298491A - Water-base curable resin composition, coating material, and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base curable resin compsn. which exhibits the improvement in resistances to water and solvents, etc., due to crosslinking, in which the compatibility of an isocyanate compd. with polymer particles is good, and which forms a coating film excellent in low-temp. flexibility by compounding polymer particles comprising a urethane polymer and a hydroxylated vinyl polymer with a polyisocyanate and a water-base medium. SOLUTION: The urethane polymer is pref. a water-base one. The hydroxylated vinyl polymer is pref. a copolymer obtd. by copolymerizing a hydroxylated acrylic monomer with another acrylic monomer. The hydroxyl value of the polymer particles is pref. 0.1-300 mgKOH/g. A self-emulsifiable polyisocyanate and/or a water-base blocked polyisocyanate is pref. as the polyisocyanate. The wt. ratio (solid basis) of the urethane polymer to the hydroxylated vinyl polymer is pref. 0.1-10.0. The molar ratio of isocyanate groups of the polyisocyanate to hydroxyl groups of the polymer particles is pref. 0.1-5.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous curable resin composition and a paint, an adhesive and the like using the same. More specifically, the present invention relates to an aqueous curable resin composition comprising a polymer particle (A) composed of a urethane polymer and a hydroxyl group-containing vinyl polymer, a polyisocyanate (B) and an aqueous medium (C). It can be widely used for applications such as paints, adhesives and the like for cement, concrete, metal, plastic, paper, leather, wood, fiber and the like.

[0002]

2. Description of the Related Art In recent years, there has been an urgent shift to water-soluble resins and aqueous resins such as aqueous emulsions due to stricter regulations on organic solvents and pollution problems such as air pollution. further,
With higher quality and use for new applications, it has become difficult for conventional aqueous dispersions to exhibit required physical properties such as water resistance and solvent resistance.

[0003] For this reason, a cross-linking agent is often used in combination to improve the above physical properties. There are various reactions in a crosslinking system, and among them, various techniques using polyisocyanate as a crosslinking agent have been proposed. For example, JP-A-61-291613, JP-A-5-148341
And JP-A-7-48429 disclose techniques using a self-emulsifying type polyisocyanate.
Also, JP-A-4-216815, JP-A-6-56
No. 953 discloses a technique using an aqueous blocked polyisocyanate in which isocyanate groups are blocked.

[0004]

However, there is a problem in that both the improvement of the crosslinking density and the flexibility of the resin are compatible. That is, when the crosslink density is increased for the purpose of improving the solvent resistance and the water resistance, there have been problems that the flexibility of the resin is lost or the original physical properties cannot be exhibited due to the deterioration of the film formation state. Further, when a polyisocyanate is blended as a crosslinking agent for the vinyl polymer, the compatibility of the polymer is poor,
This hindered the improvement of physical properties, such as cloudiness of the film and deterioration of the film formation state.

An object of the present invention is to provide a resin which has good compatibility with polyisocyanate while improving physical properties such as solvent resistance and water resistance by a crosslinking reaction, and particularly has the flexibility of a resin at a low temperature. Aim.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve such conventional problems, and as a result, the polyisocyanate is composed of a urethane polymer and a hydroxyl group-containing vinyl polymer. By combining the polymer particles, it is possible to improve the physical properties such as solvent resistance and water resistance by a crosslinking reaction, have good compatibility with the polyisocyanate, and have the flexibility of the resin at a low temperature. This led to the completion of the present invention.

That is, the present invention relates to a urethane-based polymer (a
Aqueous curing type comprising polymer particles (A) composed of at least two kinds of polymers 1) and hydroxyl group-containing vinyl polymer (a2), polyisocyanate (B) and aqueous medium (C) The present invention relates to a resin composition, a paint, and an adhesive.

Preferably, a hydroxyl group-containing vinyl polymer (a
2) is an acrylic polymer obtained by polymerizing a hydroxyl group-containing acrylic monomer and another acrylic monomer, and the polymer particles (A) preferably have a hydroxyl value of 0.1 to 30.
The present invention relates to an aqueous curable resin composition, a coating, and an adhesive wherein the polyisocyanate (B) is 0 mgKOH / g, and preferably the polyisocyanate (B) is a self-emulsifying polyisocyanate and / or an aqueous blocked polyisocyanate.

More preferably, the urethane polymer (a
1) is obtained by chain-extending a urethane prepolymer with a polyol compound, having a hydroxyl group at the molecular end, or obtained by chain-extending the urethane prepolymer with a hydrazine-based compound, and having a hydrazine structure at the molecular end. A hydroxyl group-containing vinyl polymer (a2)
Aqueous-curing type, which is a polymer having a hydroxyl group and a carbonyl group in a molecular side chain, obtained by radical polymerization of a hydroxyl group-containing vinyl monomer, a carbonyl group-containing vinyl monomer, and another vinyl monomer. The present invention relates to a resin composition, a paint, and an adhesive.

Preferably, the polymer particles (A) are obtained by emulsion polymerization of a vinyl monomer mixture containing a hydroxyl group-containing vinyl monomer in the presence of a urethane polymer (a1), Preferably, the solid content weight ratio of the urethane polymer (a1) to the vinyl polymer (a2) in the polymer particles (A) is 0.1 ≦ a1 / a2 ≦ 10.0, and preferably the polymer particles Aqueous curable resin composition wherein the ratio of the number of moles of hydroxyl groups (α) in (A) to the number of moles of isocyanate groups (β) in polyisocyanate (B) is 0.1 ≦ β / α ≦ 5.0 And paints and adhesives.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The urethane polymer (a1) of the present invention is not particularly limited, but is preferably an aqueous urethane polymer from the viewpoint of water dispersibility. The aqueous urethane-based polymer is produced, for example, as follows. That is, first, a diisocyanate and a glycol and a glycol having a carboxylic acid group for improving water dispersibility are subjected to a urethane-forming reaction to obtain a urethane prepolymer. Next, the prepolymer is neutralized and chain-extended, and water is added to obtain an aqueous urethane-based polymer. The organic solvent used in the reaction may be removed by a known method as necessary.

The diisocyanates used at this time include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates comprising these isomers, 1,6- Aliphatic diisocyanates such as hexamethylene diisocyanate, aliphatic diisocyanate such as 1,12-dodecane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 2,4,6-triisocyanate toluene, 2,
Examples thereof include triisocyanates such as 4,4'-triisocyanate diphenyl ether and tri (isocyanatephenyl) methane.

The glycols used in preparing the urethane prepolymer include low molecular weight glycols, high molecular weight glycols, polyester polyols, polycarbonate polyols, and the like. These may be used alone or in combination. May be.

Examples of low molecular weight glycols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, and octane. Examples thereof include diol, tricyclodecane dimethylol, hydrogenated bisphenol A, and cyclohexane dimethanol, and two or more of these may be mixed.

Examples of the high molecular weight glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. As the polyester polyols, those obtained by subjecting a glycol component and a dicarboxylic acid component to an esterification reaction or a transesterification reaction by a known method can be used. Further, polyester polyols obtained by ring-opening polymerization of caprolactone, hivalolactone and the like are also included.

The glycol component which can be used at this time includes the aforementioned low molecular weight glycols, and the dicarboxylic acid component includes maleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecandionic acid, terephthalic acid, Isophthalic acid, naphthalenedicarboxylic acid and the like.

Polyester polyols using an unsaturated dicarboxylic acid as the carboxylic acid component are preferred because they are expected to be functionally linked to vinyl monomers. Examples of the unsaturated dicarboxylic acid include itaconic acid, maleic acid, and phthalic acid. These dicarboxylic acids are used alone or in combination.

Glycols having a carboxylic acid group in producing a urethane prepolymer include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid,
2,2-dimethylolvaleric acid and the like.

The reaction between diisocyanate and glycol is carried out by dioxane, acetone, methyl ethyl ketone, N-
It is desirable to carry out in an organic solvent such as methylpyrrolidone and tetrahydrofuran which is inert to isocyanate groups and has high affinity for water. Further, a vinyl monomer can be used instead of the organic solvent.

Examples of the neutralizing agent for the carboxyl group include amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine, potassium hydroxide,
Examples include alkaline substances such as sodium hydroxide and ammonia.

As a chain extender of the urethane prepolymer,
Generally, polyols such as ethylene glycol and propylene glycol; ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine,
Aliphatic, alicyclic and aromatic diamines such as xylylenediamine, diphenyldiamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, hydrazine, ethylene-1,2-dihydrazine, propylene-1,3 -Dihydrazine, butylene-
1,4-dihydrazine, adipic acid dihydrazide, 1,
And hydrazine derivatives such as 3-bis (hydrazinocarboethyl) -5-isopropylhydantoin.

At this time, when a polyol is used as a chain extender, a hydroxyl group is introduced into the polymer molecule terminal of the urethane polymer (a1), and together with the hydroxyl group in the vinyl polymer (a2), the polyisocyanate (B) is used. It is preferable because a functional connection between the urethane polymer (a1) and the vinyl polymer (a2) is expected. When a hydrazine derivative is used as a chain extender, a chemical structure of —NHNH ₂ is introduced into a polymer molecular terminal of the urethane polymer (a1), and a carbonyl group-containing monomer is contained in the vinyl polymer (a2). And the amide group-containing monomer, the urethane polymer (a1) and the vinyl polymer (a
The functional connection of 2) is expected.

In the present invention, the acid value in the urethane polymer (a1) is preferably from 10 to 200 per resin solid content. When the acid value is less than 10, when the urethane prepolymer reacted in an organic solvent is converted to an aqueous solution using a neutralizing agent, a chain extender, and distilled water, agglomerates are easily formed, and the storage stability of the obtained aqueous urethane resin is increased. Also worse. On the other hand, when the acid value is 20
If it exceeds 0, the durability and water resistance of the coating film may not be obtained.

The hydroxyl group-containing vinyl polymer of the present invention (a
2) can be obtained by polymerizing a hydroxyl group-containing vinyl monomer and another acrylic monomer. The hydroxyl group-containing vinyl monomer is not particularly limited, but may be any compound containing a polymerizable unsaturated group and a hydroxyl group in one molecule. For example, β-hydroxyethyl (meth) ) Acrylic monomers containing hydroxyl groups such as acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and glycerol mono (meth) acrylate And hydroxyalkyl vinyl ethers such as butyl vinyl ether.

The vinyl monomer other than the hydroxyl group-containing vinyl monomer used in the present invention is not particularly limited, but contains a polymerizable unsaturated group in one molecule. If it is, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Hexyl methacrylate, cyclohexyl methacrylate,
Methacrylates such as nonyl methacrylate, lauryl methacrylate, and stearyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate; Acrylic monomers, esters such as maleic acid, fumaric acid, itaconic acid, aromatic vinyl compounds such as styrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, chloromethylstyrene and vinyltoluene , Heterocyclic vinyl compounds such as vinylpyrrolidone, unsaturated nitriles such as acrylonitrile and methacrylonitrile, conjugated diolefins such as butadiene and isoprene, divinylbenzene, ethylene glycol diacrylate, and ethylene glycol dimethyl. Polyfunctional vinyl monomers such as acrylate, diethylene glycol dimethacrylate, allyl methacrylate, diallyl phthalate, trimethylolpropane triacrylate, glycerin diallyl ether, polyethylene glycol dimethacrylate, and polyethylene glycol diacrylate; vinyls such as ethylene, propylene, and isobutylene Monomers, vinyl acetate, vinyl propionate, vinyl esters such as octyl vinyl ester, ethyl vinyl ether, propyl vinyl ether,
Butyl vinyl ether, vinyl ethers such as cyclohexyl vinyl ether, allyl ethers such as ethyl allyl ether, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, chlorotrifluoroethylene,
Tetrafluoroethylene, hexafluoropropylene,
Examples include halogenated olefins such as pentafluoropropylene, halogenated vinyl compounds such as perfluoro (propyl vinyl ether), fluoroacrylates, and fluoromethacrylate compounds.

Further, other vinyl monomers include amide monomers such as acrylamide, methacrylamide and n-methylol methacrylamide, amino group-containing monomers such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate, and glycidyl acrylate. Glycidyl group-containing monomers such as glycidyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid or its half ester, fumaric acid or its half ester, itaconic acid or its half ester, crotonic acid, p-vinylbenzoic acid Contains reactive polar groups such as carboxyl group-containing monomers such as acids, and vinylsilanes such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane. And vinyl monomers.

Further, a urethane polymer (a1) in which a hydrazine compound is used as a chain extender and a hydrazine structure is introduced into the molecule, a carbonyl group-containing vinyl monomer and a hydroxyl group-containing vinyl monomer as vinyl monomers. When a vinyl monomer is used and a carbonyl group- and hydroxyl group-containing vinyl polymer (a2) is used in the molecule, a room temperature crosslinking reaction can be introduced between both polymers, and further improvement in physical properties is expected. preferable.

The carbonyl group-containing vinyl monomer means a monomer having a keto group, such as acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl butyl ketone, diacetone acrylate,
Examples include acetonitrile acrylate, acetoacetoxyethyl (meth) acrylate, vinyl acetophenone, vinyl benzophenone, and the like. Compounds having an ester bond or a carboxyl group are not included in these. These vinyl monomers can be freely used in combination according to the use and required physical properties.

In the present invention, the polymer particles (A) may have any structure as long as they are composed of a urethane polymer (a1) and a hydroxyl group-containing vinyl polymer (a2). Examples thereof include a structure in which (a1) and (a2) are bonded, and a multilayer structure such as a core-shell.

Examples of the method for producing the polymer particles (A) include a method in which a vinyl monomer mixture containing a hydroxyl group-containing vinyl monomer is emulsion-polymerized in the presence of a urethane polymer (a1); When manufacturing a prepolymer, a vinyl monomer is used for a part or all of an organic solvent, and after making this aqueous, the vinyl monomer is polymerized to form a urethane polymer and a vinyl polymer. Examples of the method include a method for obtaining a composite, a method in which a urethane prepolymer is dissolved in a vinyl monomer group, and polymerization and an elongation reaction are simultaneously performed. Among these production methods, a method in which a vinyl monomer mixture containing a hydroxyl group-containing vinyl monomer is emulsion-polymerized in the presence of a urethane-based polymer in consideration of the ease of controlling the reaction is preferred.

The polymer particles (A) thus obtained
Aqueous dispersion is a film in which the polymers are homogeneously mixed with each other compared to a simple mixture of a urethane-based polymer and a vinyl-based polymer.The transparency of the film, the water resistance, and the film after immersion in water A film excellent in many points such as the mechanical strength and the elongation retention of the film is formed.

At this time, although not always necessary, a surfactant (emulsifier) can be used in the range of 0 to 10 parts by weight based on 100 parts by weight of the vinyl monomer. At this time, a conventionally known surfactant (emulsifier) can be used. Examples of the surfactant include alkyl sulfate, alkane sulfonate, alkyl benzene sulfonate, alkyl aryl polyether sulfate, (di) alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylphenyl sulfate, and the like. Nonionic emulsifiers: Nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, etc .: such as cetyltrimethylammonium bromide, laurylpyridinium chloride, etc. Novel cationic emulsifiers: sodium vinyl sulfonate, sodium styrene sulfonate, polyoxyethylene ammonium (meth) acrylate, (meth) acrylic acid Sodium polyoxyethylene sulfonate, ammonium polyoxyethylene alkenylphenyl sulfonate, sodium polyoxyethylene alkenylphenyl sulfate, sodium allylalkyl sulfosuccinate, sodium polyoxypropylene sulfonate (meth) acrylate, 2-hydroxyethyl (meth) Anionic reactive emulsifiers such as acryloyl phosphate: Nonionic reactive emulsifiers such as polyoxyethylene alkenyl phenyl ether and polyoxyethylene (meth) acryloyl ether. In addition, as a commercially available reactive emulsifier, for example, Aqualon HS-10, New Frontier A-229E (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SE-3N, SE-5N, SE- 10N, S
E-20N, SE-30N [Asahi Denka Kogyo Co., Ltd.
Manufacture], AntoxMS-60, MS-2N, RA-11
20, RA-2614 [manufactured by Nippon Emulsifier Co., Ltd.], Eleminor JS-2, RS-30 [manufactured by Sanyo Chemical Industries, Ltd.], Latemul S-120A, S-180A, S
Anionic reactive surfactants, such as -180 [manufactured by Kao Corporation], Aqualon RN-20, RN-30, RN-
50, New Frontier N-177E [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], Adecaria Soap NE-10, NE-
20, NE-30, NE-40 [Asahi Denka Kogyo Co., Ltd.
RMA-564, RMA-568, RMA-11
14 [manufactured by Nippon Emulsifier Co., Ltd.], NK ester M-2
Nonionic reactive surfactants such as 0G, M-40G, M-90G, and M-230G (all manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned. Of course, other commercially available surfactants can also be used, and a plurality of these surfactants can be used in combination.

In addition to the emulsifier, a dispersion stabilizer, a radical polymerization initiator and the like can be used. As the dispersion stabilizer, for example, polyvinyl alcohol, cellulose ether,
Starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide,
A synthetic or natural water-soluble polymer such as a water-soluble acrylic resin may be used, and one or a mixture of two or more thereof may be used.

As the radical polymerization initiator, for example,
Potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, azobisisobutyronitrile and its hydrochloride, and the like, and organic peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, etc. It can be used as needed.
Further, a known redox initiator using a combination of these persulfates or peroxides, metal ions such as iron ions, and reducing agents such as sodium sulfoxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid may also be used. Can be.

The temperature at the time of the polymerization may be in the range performed by a known technique, and the emulsion polymerization is performed under normal pressure or under pressure when a gaseous vinyl monomer is used. In the aqueous curable resin composition of the present invention, the hydroxyl value in the polymer particles (A) can be freely set depending on the application and the required performance. It is desirable to be in the range of 1 to 300 mgKOH / g.

In the aqueous curable resin composition of the present invention,
The ratio of the urethane polymer (a1) to the hydroxyl group-containing vinyl polymer (a2) in the polymer particles (A) is not particularly limited, but is 0.1 ≦ a1 / a2 in terms of the solid content weight ratio.
The range of ≦ 10.0 is preferable, and it can be freely designed in consideration of use, required performance, cost and the like. By adjusting the ratio of the urethane polymer (a1) and the vinyl polymer (a2) within the scope of the present invention in accordance with cost, application, required performance, etc., the characteristics of the urethane resin can be emphasized, The characteristics of the resin can be emphasized, and the resin can be used in a wide range of fields as a coating agent, an adhesive and the like.

The polyisocyanate (B) of the present invention is not particularly limited as long as it has at least one isocyanate group in the molecule and can be dispersed in water, but the crosslinking reaction with the polymer particles (A) is not limited. In consideration of the progress, compatibility, and workability of the resin, those which are easily miscible with water are preferable, and are self-emulsified by modification with at least one or more hydrophilic components such as polyethylene oxide, carboxyl group, and sulfonic acid group. Type polyisocyanates and aqueous block isocyanates are preferred.

As a method for mixing the polyisocyanate (B) of the present invention with the polymer particles (A), the polyisocyanate (B) is blended into an aqueous dispersion of the polymer particles (A), For example, a method of forcibly dispersing or a method of dispersing using an emulsifier instead of the mechanical dispersion described above may be used.

The polyisocyanate may be added to the aqueous dispersion of polymer particles (A) immediately before use as a paint, an adhesive or the like, regardless of the timing of addition to the aqueous dispersion of polymer particles (A). A well-prepared aqueous dispersion may be used. At this time, heating may be performed if necessary.

The self-emulsifying polyisocyanate can be obtained, for example, by introducing a hydrophilic group and a hydrophobic group having at least one active hydrogen group capable of reacting with an isocyanate group into the polyisocyanate. Introducing not only hydrophilic groups but also hydrophobic groups is because, when polyisocyanate is dispersed in water, the reaction between water molecules around it and unreacted NCO groups near it is sterically hindered. This is for obtaining the effect of suppressing the surface chemistry based on the target or its lipophilicity. Examples of the hydrophobic group include a higher alcohol having at least one active hydrogen group and a hydroxyl group-containing fatty acid ester.

The polyisocyanate used for the self-emulsifying type polyisocyanate includes, for example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, and aromatic diisocyanates comprising isomers thereof. Aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,12-dodecane diisocyanate, cycloaliphatic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and norbornane diisocyanate; 2,4,6-triisocyanate toluene; , 4,4'-Triisocyanate diphenylate And triisocyanates such as ter and tri (isocyanatephenyl) methane. Further, an isocyanate group-terminated compound obtained by reacting a polyisocyanate with an active hydrogen group-containing compound,
Alternatively, there may be mentioned the reaction of these compounds, for example, adduct-type polyisocyanate, uretdionation reaction, isocyanuration reaction, carbodiimidation reaction, uretonimine reaction, buretization reaction and the like, and isocyanate-modified products, and mixtures thereof. Among these polyisocyanates, aliphatic or alicyclic polyisocyanates are preferable from the viewpoints of water dispersion stability, stability of isocyanate groups after water dispersion, and non-yellowing, among which heat resistance, crosslinkability, etc. In this respect, isocyanurate ring-containing polyisocyanates having an average number of NCO functional groups of 2 or more are preferred.

Such an isocyanurate ring-containing polyisocyanate can be obtained, for example, by converting a raw material polyisocyanate into a tertiary amine, an alkyl-substituted ethyleneimine,
Known uretdionation catalysts and / or isocyanuration catalysts such as tertiary alkyl phosphines, metal salts of acetyl acene, and metal salts of various organic acids, and, if necessary, a cocatalyst may be used in the presence or absence of a solvent. Liquid polyol or DO at a reaction temperature of usually 0 to 90 ° C in the presence of
Manufactured in a plasticizer such as P.

Examples of the cocatalyst include a phenolic hydroxyl group-containing compound and an alcoholic hydroxyl group-containing compound. Examples of the solvent include aromatic solvents such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, propylene glycol methyl ether acetate, and ethyl-3-ethoxypropionate. Solvents that are inert to isocyanate groups, such as glycol ether esters, are exemplified.

The reaction can be stopped by inactivating the catalyst with a reaction terminator. Examples of the reaction terminator include phosphoric acid, methyl paratoluenesulfonate, sulfur and the like.

Examples of the hydrophilic group of the self-emulsifying polyisocyanate include ionic groups such as cations and anions, and nonionic groups. Examples of the nonionic compound for introducing a nonionic group into the polyisocyanate include a polyalkylene ether alcohol and a polyoxyalkylene fatty acid ester.

The active hydrogen-containing compound used as an initiator in the production of the polyalkylene ether alcohol includes, for example, methanol, n-butanol, cyclohexanol, phenol, ethylene glycol, propylene glycol, aniline, trimethylolpropane, glycerin and the like. Can be Among them, it is preferable to use a lower alcohol from the viewpoint of aqueous dispersion stability.

The fatty acids used as initiators in the production of polyoxyalkylene fatty acid esters include acetic acid, propionic acid, butyric acid and the like. Of these, lower fatty acids are preferably used from the viewpoint of aqueous dispersion stability.

The number of alkylene oxide chains present in the polyalkylene ether alcohol, polyoxyalkylene fatty acid ester and the like is generally 3 to 90, preferably 5 to 50. The alkylene oxide chain may be composed entirely of ethylene oxide chains, or may be a combination of an ethylene oxide unit and another alkylene oxide unit such as a propylene oxide unit in the entire alkylene oxide chain. Taking into account the dispersibility, those containing at least 70% of ethylene oxide units are preferred.

Examples of the ionic compound for introducing an ionic group into the polyisocyanate include anionic compounds such as a fatty acid salt, a sulfonate, a phosphate, and a sulfate, a primary amine salt and a secondary amine. And cationic compounds such as salts, tertiary amine salts, quaternary ammonium salts and pyridinium salts, and amphoteric compounds such as sulfobetaine.

Examples of higher alcohols for introducing a hydrophobic group into a polyisocyanate include octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, and the like.
Examples include pentadecyl alcohol, cetyl alcohol, cinnamyl alcohol and the like.

As the fatty acid as a raw material of the fatty acid ester for introducing a hydrophobic group into the polyisocyanate,
α-oxypropionic acid, oxysuccinic acid, dioxysuccinic acid, ε-oxypropane-1,2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoelaidic acid,
Lisinostearolic acid, salicylic acid, mandelic acid, and the like, and as the hydroxyl group-containing compound,
Examples include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, dodecyl alcohol, lauryl alcohol and the like.

The self-emulsifying type polyisocyanate of the present invention can be prepared by a known method, generally in the absence of a solvent in the range of 50 to 13%.
Although it is produced at a moderately elevated temperature of 0 ° C., inert solvents and catalysts commonly used in the urethane industry can be used if necessary.

The self-emulsifying type polyisocyanate can improve the water dispersion stability by introducing a hydrophilic chain, and further introduces a lipophilic chain having an appropriate length in consideration of the balance with the hydrophilic chain. By doing so, the reaction between isocyanate groups and water in water can be surface-chemically suppressed.

Other substances can be mixed with the self-emulsifying type polyisocyanate as required. For example, antioxidants, ultraviolet absorbers, heat resistance improvers, colorants, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, catalysts, and the like can be added.

The above self-emulsifying polyisocyanate is
By mixing with water, an aqueous dispersion can be easily obtained. The resulting aqueous dispersion has a very good adhesion, because the isocyanate groups present in a relatively stable manner even after being dispersed in water react with the active hydrogen groups present on the surface of the base material. Agent can be obtained.

After a considerable time has elapsed since the polyisocyanate was dispersed in water, even after the isocyanate group disappeared, polyisocyanate particles having a particle size of about 0.1 to 0.3 μm stably existed as an emulsion state. Therefore, a film obtained by applying this and drying at room temperature or by heating is hard and tough. Therefore, it can be used as a film or sheet, or as a coating agent for various substrates. When importance is attached to the adhesion to the substrate, it is desirable to apply and use in a state where the isocyanate group is present.

In order to obtain an aqueous blocked isocyanate of the polyisocyanate (B) in the present invention, the blocked isocyanate is dispersed in water.
For example, a method of dispersing a blocked isocyanate using a highly hydrophilic blocking agent such as sodium bisulfite, a method of modifying a part of a polyisocyanate with a compound having a hydrophilic group, and dispersing in water are exemplified.

Modification of the polyisocyanate with a hydrophilic group can be performed by adding a hydrophilic polyol such as polyethylene glycol or a glycol having a hydrophilic group such as a carboxylic acid such as dimethylolpropionic acid or dimethylolbutanoic acid to the polyisocyanate. The reaction is carried out in the presence of a catalyst, if necessary.

Examples of the polyisocyanate used in the aqueous dispersion of the blocked isocyanate include those similar to those used in the above-mentioned self-emulsifying polyisocyanate. In these polyisocyanates, the isocyanate groups are blocked by a blocking agent to form blocked isocyanates. Examples of the blocking agent include dimethyl malonate, diethyl malonate, methyl acetoacetate,
Active methylene compounds such as ethyl acetoacetate and acetylacetone, formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketoxime,
Oxime compounds such as cyclohexanone oxime and the like may be mentioned, and these may be used alone or as a mixture of two or more.

The blocking reaction can be carried out irrespective of the presence or absence of a solvent. When a solvent is used, it is necessary to use a solvent inert to isocyanate groups. As an inert solvent for isocyanate groups,
Those used in general urethane-forming reactions can be used. When a solvent is used, after the blocked isocyanate is dispersed in water, the solvent may be removed by a known technique if necessary. During the blocking reaction,
Organic metal salts such as tin, zinc, and lead, and tertiary amines may be used. The reaction can be generally performed at -20 ° C to 150 ° C. If the isocyanate group is not blocked, it reacts with water or an active hydrogen-containing compound during storage and cannot participate in crosslinking. Therefore, it is preferable that substantially all of the isocyanate group is blocked.

The blocked isocyanate obtained as described above is dispersed in water by using an emulsifier or a protective colloid such as polyvinyl alcohol if necessary. At this time, an emulsifying device such as a homomixer or a homogenizer may be used to disperse the blocked isocyanate in water.

The aqueous blocked isocyanate thus obtained is blended with the aqueous dispersion of the polymer particles (A) to give the aqueous curable resin composition of the present invention. By heating the aqueous curable resin composition during use, the blocking agent is dissociated from the latent blocked isocyanate,
A film having excellent physical properties is formed by a crosslinking reaction between the isocyanate group and the hydroxyl group in the polymer particles (A).

In the aqueous curable resin composition of the present invention,
Since the reaction of the polyisocyanate can react not only with the hydroxyl groups in the polymer particles (A) but also with the water of the solvent, the number of moles (α) of the hydroxyl groups in the polymer particles (A) and the isocyanate in the polyisocyanate (B) When only the reactivity of the group or the latent blocked isocyanate group (β) is considered, it is desirable that the ratio (β / α) of these moles is 1 or more. The range is preferably 0.1 ≦ β / α ≦ 5.0, more preferably 0.5 ≦ β / α ≦ 2.0. The present invention is an aqueous dispersion of polymer particles comprising a urethane-based polymer and a vinyl-based polymer containing a hydroxyl group, by blending a polyisocyanate, during the film formation in the polymer particles or between the particles functional. Bonding is developed, and the performance of the cured product can be significantly improved. When a self-emulsifying polyisocyanate is used as the polyisocyanate, the isocyanate group reacts with the hydroxyl group in these polymer particles by mixing with the aqueous dispersion of the polymer particles immediately before use, so that adhesion and solvent resistance are improved. And so on, which are suitable as coatings and adhesives. When an aqueous blocked isocyanate is used as the polyisocyanate, the blocked isocyanate is dissociated by heating at the time of use, and quickly reacts with the hydroxyl group in the polymer particles.

The aqueous medium (C) of the present invention is basically water, and may contain a solvent. Examples of the solvent include the aromatic, ketone, ester, and glycol ether ester solvents described above.

The aqueous curable resin composition of the present invention can be used as it is, but various additives can be added according to the use and purpose. Additives include pigments, fillers, aggregates, dispersants, wetting agents, thickeners, rheology control agents, defoamers, plasticizers, film-forming aids, organic solvents, preservatives, pH adjusters, Examples include a rust agent, an antioxidant, and an ultraviolet absorber, and these can be used in an appropriate combination.

[0066]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to only the following examples. In the following, parts and% are values based on weight.

Production Example 1 (Production of polymer particles) 1,780 g of 1,6-hexanediol, 25 adipic acid
45 g and 2,2-dimethylolpropionic acid 567
g, and the mixture was heated to 170 ° C. and reacted at this temperature for 23 hours to obtain a polyester polyol (I) having an OH value of 60 and an acid value of 60.

1815 g of this polyester polyol
Was diluted by adding methyl ethyl ketone. 240 g of this polyester polyol solution (I), 220 g of methyl ethyl ketone, 2,2-dimethylolpropionic acid 3
0 g and cyclohexane dimethanol 27 g at 70 ° C.
After sufficiently stirring and mixing at, 236 g of 4,4′-dicyclohexylmethane diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted for 6 hours, and then cooled to 30 ° C. to obtain a urethane prepolymer solution.

This polyurethane prepolymer solution was gradually poured under high-speed stirring into an aqueous amine solution in which 21 g of an 80% aqueous hydrazine solution and 40 g of triethylamine were dissolved in 1500 g of ion-exchanged water in advance to obtain a viscous, translucent product. Was. After removing the solvent at 55 ° C. under reduced pressure, the concentration was adjusted by adding ion-exchanged water, the nonvolatile content was 23.7%, and the viscosity (BM viscometer, 60 rpm, 25 rpm).
C) 23 cps, a translucent aqueous urethane polymer (a1) having a pH of 8.4 was obtained.

Next, a vinyl polymer was produced using the following materials. Polymerizable monomers 2-ethylhexyl acrylate 265 g Styrene 100 g Methyl methacrylate 65 g Acrylic acid 10 g β-hydroxyethyl methacrylate 50 g Diacetone acrylamide 10 g Surfactants Newcol 707SF (solid content 30%) * 1) 50 g Ion exchange 360 g of water Polymerization initiator: 2.5 g of ammonium persulfate * 1) Special anionic emulsifier manufactured by Japan Emulsifier Co., Ltd. 30 g of surfactant in a four-necked flask, 21 ion-exchanged water
After stirring 0 g and 1054 g of the aqueous urethane polymer (a1), stirring was started, the temperature was raised to 80 ° C. in a nitrogen stream, and then a polymerization initiator was added. Then polymerizable monomers 500
g, 20 g of a surfactant, and 150 g of ion-exchanged water were mixed to prepare a monomer pre-emulsion. This monomer pre-emulsion was dropped into the above flask over 3 hours. At this time, the reaction temperature was kept at 80 ± 3 ° C. After completion of the dropwise addition, the reaction was continued under stirring while maintaining the same temperature range for 2 hours.
H8-9, nonvolatile content 38.0%, viscosity 200
An aqueous dispersion of polymer particles having a cps of pH 8.5 was obtained.

Production Example 2 (Production of polymer particles) Further, an aqueous dispersion of polymer particles was obtained in the same manner as in Production Example 1, using the raw materials shown in Table 1.

Comparative Production Examples 1 and 2 In Production Example 1, emulsion polymerization was carried out using the raw materials shown in Table 1 under the same reaction conditions as in Production Example 1 to synthesize an acrylic emulsion and disperse the resin in water. I got a body.

Comparative Production Examples 3 and 4 The aqueous urethane polymer (a1) was added to the aqueous resin dispersions of Comparative Production Examples 1 and 2 at the ratios shown in Table 1 to obtain aqueous resin dispersions.

[0074]

[Table 1]

Example 1 Aqueous dispersion of polymer particles 100 obtained in Production Example 1 above
Then, 10 g of Aquanate 210 (a self-emulsifying polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the resulting mixture and mixed well to obtain an aqueous curable resin composition.

Example 2 10 g of Elastron BN-08 [aqueous blocked isocyanate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] and 10 g of Elastron Catalyst 64 [Daiichi Kogyo Seiyaku (100 g) were added to 100 g of the aqueous resin dispersion obtained in Production Example 1 above. 0.5 g of a blocked isocyanate manufactured by Co., Ltd.] and mixed well to obtain an aqueous curable resin composition.

Comparative Example 1 The aqueous resin dispersion obtained in Production Example 1 was used as Comparative Example 1 as it was. Comparative Example 2 The aqueous resin dispersion obtained in Comparative Production Example 1 was blended in the same manner as in Example 1 to obtain Comparative Example 2.

Comparative Example 3 The aqueous resin dispersion obtained in Comparative Production Example 1 was mixed in the same manner as in Example 2 to obtain Comparative Example 3.

Comparative Example 4 The aqueous resin dispersion obtained in Comparative Production Example 3 was blended in the same manner as in Example 1 to obtain Comparative Example 4.

Comparative Example 5 The aqueous resin dispersion obtained in Comparative Production Example 3 was blended in the same manner as in Example 2 to obtain Comparative Example 5.

Immediately after mixing, the aqueous resin dispersion obtained as described above was tested by the following test method. <Film physical properties> Films were prepared using the aqueous resin dispersions (Examples 1 and 2 and Comparative Examples 1 to 5) obtained by the following formulations, and were subjected to the following tests and test methods. [Test Method] (1) Transparency of film: A sample was poured on a glass plate, dried for 3 days, peeled off the glass plate, turned upside down, and dried for 4 days (when a block polyisocyanate was used, further 140 ° C. For 30 minutes). The sample was collected so that the film thickness after drying was 0.2 mm. The total transmittance TL of the collected test pieces was measured under the following conditions, and the transparency of the film was evaluated.

Turbidity meter: Turbidity meter N manufactured by Nippon Denshoku Industries Co., Ltd.
DH-300A Measurement light source: Halogen lamp Light receiving element: Silicon photocell based on JIS K7105 Measurement area: Transmission 12φ TL: Total transmittance (%) Evaluation criteria ○: Total transmittance is 85% or more.

Δ: The total transmittance is 70% or more and less than 85%. X: Total transmittance is less than 70%. (2) Gel fraction: The gel fraction was measured as an acetone-insoluble component. Pour the sample on a glass plate and dry for 3 days.
Peel off the glass plate, turn it over and dry it for 4 days (additional 140 if using blocked polyisocyanate)
(Heat-treated at 30 ° C. for 30 minutes). The sample was collected so that the film thickness after drying was 0.5 mm.
The test piece was cut into a square of 0 mm.

Next, the weight (G0) of the test piece before immersion in acetone was measured in advance, and the test piece was placed in an acetone solution at room temperature for 24 hours.
The acetone-insoluble portion of the test piece after immersion for hours was separated, and the weight (G1) after drying at 110 ° C. for 1 hour was measured, and the gel fraction was determined according to the following method.

[0085] G0: Weight of test piece before immersion in acetone G1: Dry weight of insoluble portion of test piece after immersion in acetone (3) Coating solvent resistance: A sample is applied on a glass plate with a 3 mil applicator, and at room temperature for 3 days The test piece was dried (when a blocked polyisocyanate was used, heat treatment was further performed at 140 ° C. for 30 minutes). Rubbing was performed 100 times on the resin-coated surface of the obtained test piece with a cotton swab impregnated with an acetone or toluene solution, and the presence or absence of deterioration of the coated surface was observed.

Evaluation criteria ：: No abnormality was found in the film. Δ: Deterioration occurred on the surface and inside of the film, and desorption from the glass plate was slightly observed.

×: Degraded to the inside of the film, and remarkably desorbed. (4) Water resistance of the film: A sample is coated on a glass plate with a 3 mil applicator and dried at room temperature for 3 days.
(Heat treatment was performed for 0 minutes) to obtain a test piece.

The obtained test piece was immersed in water at room temperature for 7 days, the turbidity of the test piece before and after immersion in water was measured with a turbidimeter, and the degree of change in turbidity was determined as W value. The deterioration (whitening) of the film due to water immersion was evaluated.

Turbidity meter: Turbidity meter ND manufactured by Nippon Denshoku Industries Co., Ltd.
H-300A Measurement light source: Halogen lamp Light receiving element: Silicon photocell based on JIS K7105 Measurement area: Transmission 12φ The degree of change in turbidity and the turbidity before and after immersion in water were determined according to the following equations.

[0090] TL: Total transmittance (%) DF: Diffuse transmittance (%) H0: Turbidity of the test piece before immersion in water H1: Turbidity of the test piece after immersion in water Evaluation criteria The degree of change in turbidity W value was evaluated in the following three stages.

：: Turbidity change degree W value is less than 5. Δ: The turbidity change degree W value is 5 or more and less than 30. X: The turbidity change degree W value is 30 or more. (5) Film water absorption: The sample was poured on a glass plate,
After drying for 3 days, it was peeled off from the glass plate, turned upside down, and dried for 4 days (when a blocked polyisocyanate was used, it was further heated at 140 ° C. for 30 minutes) before use. Samples were collected so that the film thickness after drying was 0.5 mm, cut into 20 mm squares, and measured for weight (W0)
A test piece was prepared.

The test piece was immersed in water at room temperature for 7 days, pulled up and lightly wiped off the moisture on the film surface, and then weighed (W1). Further, the film was dried at 110 ° C. for 1 hour, allowed to cool, and the weight was measured (W2). The film water absorption was determined by the following formula.

[0093] W0: Weight of test film before immersion in water W1: Weight of test film after immersion in water W2: Weight of test film after immersion in water (6) Film strength, elongation: Pour sample onto glass plate, After drying for 3 days, it was peeled off from the glass plate, turned upside down, and dried for 4 days (when a blocked polyisocyanate was used, it was further heated at 140 ° C. for 30 minutes) before use. The sample was collected so that the film thickness after drying was 0.5 mm. These films were punched out into a JIS No. 3 dumbbell mold, and the breaking strength in a tensile test was measured under the following conditions. Elongation at break (%)
And After the test piece was immersed in water at room temperature for 24 hours, the film strength and elongation were measured in a 20 ° C. atmosphere.

Tensile tester: Autograph A manufactured by Shimadzu Corporation
G-5000C Tensile speed (crosshead speed): 200 mm / min Distance between chucks: 60 mm Measurement temperature: -20 ° C., 20 ° C. [Test results] As can be seen from Table 2, the aqueous curable resin of the present invention. The coating agent containing the composition has excellent water resistance, solvent resistance, flexibility of the film at a low temperature, retention rate of strong elongation after immersion, etc. as compared with other aqueous resin dispersions. Become.

[0095]

[Table 2]

<Physical Properties of Coating Film> Each of the aqueous curable resin compositions obtained in the following formulations was used to prepare the following paint formulation, and to prepare an elastic coating agent (Examples 3 and 4, Comparative Examples 6, 7, and 8). ) Was prepared.

Example 3 The aqueous resin dispersion obtained in Production Example 1 was converted into a paint with the following composition, and Aquanate 210 [a self-emulsifying polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.] was added thereto and mixed well. And the paint was obtained.

Example 4 The aqueous resin dispersion obtained in Production Example 1 was used in Example 3.
And elastron BN-08 [aqueous blocked isocyanate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] and Elastron Catalyst 64 [catalyst for blocked isocyanate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] are added to obtain a paint. Was.

Comparative Example 6 The aqueous resin dispersion obtained in Production Example 1 was directly used as a paint. Comparative Example 7 The aqueous resin dispersion obtained in Comparative Production Example 3 was blended in the same manner as in Example 3.

Comparative Example 8 The aqueous resin dispersion obtained in Comparative Production Example 3 was blended in the same manner as in Example 4.

The water-curable coating composition obtained as described above was tested immediately after blending by the following test method. [Blending] Taipaque R-930 * 2) 100.0 Hi-Metroze 90SH-15000 * 3) 0.6 Primal 850 * 4) 1.0 5% potassium tripolyphosphate 2.0 Neugen EA-120 * 5) 0 Adecanol SX-568 * 6) 2.5 Ethylene glycol 10.0 Water 35.2 28% ammonia water 1.0 The above mixture was dispersed with a high-speed disper, and the following mixture was added. Aqueous resin dispersion * 7) 401.3 Xylene 6.6 Adecanol UH-420 / water = 1/2 * 8) Adjusted by paint viscosity Polyisocyanate / Blocked polyisocyanate 10% amount of aqueous resin dispersion Blocked polyisocyanate catalyst 0.5% amount of fat dispersion Total 561.2 N.P. V. (%) 47.3 PVC (%) 15.2 PWC (%) 39.6 * 2) Rutile type titanium oxide: Ishihara Sangyo Co., Ltd. * 3) Methyl cellulose: Shin-Etsu Chemical Co., Ltd. * 4) Polycarboxylic acid * 5) Surfactant: Daiichi Kogyo Seiyaku Co., Ltd. * 6) Defoamer: Asahi Denka Co., Ltd. * 7) Non-volatile content of aqueous resin dispersion ( %) * 8) Thickener: Asahi Denka Co., Ltd. [Test Method] Gloss of coating film: applied to a glass plate with a 3 mil applicator and dried for 1 day (Example 2 and Comparative Example 3 had an additional 14%).
Measure the reflectance at 60 ° at 0 ° C. for 30 minutes (%). JIS A6910: Elongation: The coating thickness is about 1 m when dry
m was prepared, and then cured according to the JIS elongation test method and punched out with a No. 2 dumbbell to obtain a test piece. [Application → curing for 7 days → curing for 7 days on back side → (140 ° C. × 30 minutes further in Example 2 and Comparative Example 3) → punching] Also, the test piece immersed in water at room temperature for 24 hours was measured.

Adhesion strength: Acridic 53-448 (manufactured by Dainippon Ink and Chemicals, Inc.) was applied as a primer, dried for 3 hours, and the sample was applied according to the test method.
Test after curing for 4 days (Example 2 and Comparative
(40 ° C. × 30 minutes), the four sides of the specimen used for the adhesion strength after water immersion were coated with a vinyl chloride resin paint three days before the end of curing. The adhesive used was a two-part epoxy adhesive.

Resistance to repeated action of heating and cooling: (20
18 hours in ± 2 ° C water → 3 hours at −20 ± 3 ° C → 50 ± 3 ° C
3 hours) × 10 cycles Impact resistance: in accordance with JIS elongation test method Weather resistance: same as above Coating strength: JIS A6910 The coating strength at the time of measuring the elongation is indicated.

Accelerated weathering resistance: The same coating film as that whose elongation was measured was irradiated with a standard weather meter for 500 hours, and the coating film elongation at 20 ° C. and −10 ° C. was measured. [Test Results] As can be seen from Table-3, the paint prepared by blending the water-curable resin composition of the present invention and the pigment has good weather resistance, does not deteriorate in the strength and elongation of the coating film even after being immersed, and is repeatedly heated and cooled. It is resistant to action and exhibits excellent adhesive properties.

[0105]

[Table 3]

<Adhesive Properties> Using the respective aqueous curable resin compositions obtained as described above, the following formulation was carried out to prepare adhesives (Example 5, Comparative Examples 9, 10, and 11).

Example 5 20 g of calcium carbonate was added to 100 g of the aqueous resin dispersion obtained in Production Example 2 above.
10 g (self-emulsifying polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added and mixed well to obtain an adhesive.

Comparative Example 9 20 g of calcium carbonate was added to 100 g of the aqueous resin dispersion obtained in Production Example 2 and mixed well to obtain an adhesive.

Comparative Example 10 The aqueous resin dispersion obtained in Comparative Production Example 2 was mixed in the same manner as in Example 5 to obtain an adhesive.

Comparative Example 11 The aqueous resin dispersion obtained in Comparative Production Example 4 was mixed in the same manner as in Example 5 to obtain an adhesive.

The adhesive containing the aqueous curable composition obtained as described above was tested immediately after blending by the following test method. <Adhesion condition> Adhering agent: Hip / hip (saw board, moisture content 9%) Coating amount: 260 g / m ² Pressing: 10 kg / cm ² , 24 hours, 20 ° C Curing: 3 days or more [Measurement conditions] In accordance with the JIS K-6852 test method for compressive shear adhesive strength of an adhesive.

Table 4 shows the test results.

[0113]

[Table 4]

[Test Results] As can be seen from Table 4, the adhesive of the present invention has excellent durability and water resistance.

[0115]

The aqueous curable composition of the present invention is excellent in solvent resistance, water resistance and the like, and particularly has the flexibility of resin at low temperature, so that it can be used in cement, concrete, metal, plastic, paper, leather, wood. Which can be widely used for paints, coatings, adhesives, etc. of fibers and the like.

Claims (13)

[Claims] 1. A polymer medium (A) comprising at least two kinds of polymers, a urethane polymer (a1) and a hydroxyl group-containing vinyl polymer (a2), a polyisocyanate (B), and an aqueous medium ( And C) an aqueous curable resin composition comprising: 2. The composition according to claim 1, wherein the hydroxyl group-containing vinyl polymer (a2) is an acrylic polymer obtained by polymerizing a hydroxyl group-containing acrylic monomer and another acrylic monomer. . 3. The polymer particles (A) have a hydroxyl value of from 0.1 to 0.1.
3. The composition according to claim 1, wherein the composition is 300 mgKOH / g. 4. The composition according to claim 1, wherein the polyisocyanate (B) is a self-emulsifying type polyisocyanate. 5. The composition according to claim 1, wherein the polyisocyanate (B) is an aqueous blocked polyisocyanate. 6. A urethane polymer (a1) obtained by chain-extending a urethane prepolymer with a polyol compound.
The composition according to any one of claims 1 to 5, having a hydroxyl group at a molecular terminal. 7. The urethane-based polymer (a1) is a urethane-based polymer having a hydrazine structure at a molecular terminal, obtained by elongating a urethane prepolymer with a hydrazine-based compound, and a hydroxyl-containing vinyl-based polymer. (A2)
It is a vinyl monomer having a hydroxyl group and a carbonyl group in the molecular side chain obtained by radical polymerization of a hydroxyl group-containing vinyl monomer, a carbonyl group-containing vinyl monomer, and another vinyl monomer. The composition according to claim 1. 8. The polymer particles (A) obtained by emulsion polymerization of a vinyl monomer mixture containing a hydroxyl group-containing vinyl monomer in the presence of a urethane polymer (a1). 7
A composition according to any one of the preceding claims. 9. The weight ratio of the solid content of the urethane polymer (a1) to the vinyl polymer (a2) in the polymer particles (A) is 0.1 ≦ a1 / a2 ≦ 10.0. The composition according to any one of claims 1 to 8. 10. The ratio of the number of moles of hydroxyl groups (α) in the polymer particles (A) to the number of moles of isocyanate groups (β) in the polyisocyanate (B) is 0.1 ≦ β / α ≦ 5.0. The composition according to any one of claims 1 to 9, which is 11. A polymer medium (A) comprising at least two kinds of polymers, a urethane polymer (a1) and a hydroxyl group-containing vinyl polymer (a2), a polyisocyanate (B) and an aqueous medium ( And C) a coating containing an aqueous curable resin composition comprising: 12. A polymer particle (A) comprising at least two kinds of polymers, a urethane polymer (a1) and a hydroxyl group-containing vinyl polymer (a2), a polyisocyanate (B) and an aqueous medium ( An adhesive comprising an aqueous curable resin composition comprising: C). 13. A polymer medium (A) comprising at least two kinds of polymers, a urethane polymer (a1) and a hydroxyl group-containing vinyl polymer (a2), a polyisocyanate (B) and an aqueous medium ( A coating agent comprising an aqueous curable resin composition comprising: