JP2005255833A - One-component aqueous resin composition and aqueous coating agent composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cold-setting, one-component aqueous resin composition which is excellent in water resistance and solvent resistance despite of being an aqueous resin and shows a good adhesion to a plastic surface. <P>SOLUTION: Either (x) a polymerizable unsaturated monomer having a ketotic carbonyl group is polymerized with (A) an aqueous polyurethane having at least two ketonic carbonyl groups within a molecule or (X) a water dispersion of a vinyl monomer copolymer containing ketonic carbonyl groups is added to (A) the aqueous polyurethane; and (e) a hydrazide compound having at least two hydrazino groups within a molecule is further added. Here, (A) the aqueous polyurethane is obtained from (a) an organic polyisocyanate, (b) a polyol compound containing at least two NCO-group-reactive active hydrogens, and (c) a carbonyl group-containing active hydrogen compound containing a ketonic carbonyl group and at least two NCO-group-reactive active hydrogens. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a one-part water-based resin composition and a water-based coating composition using the same, and more specifically, a coating material for building interior and exterior, a film coating agent using a room temperature-curable aqueous resin, The present invention relates to a one-component aqueous resin composition that can be suitably used for an ink binder and the like, and an aqueous coating composition using the same.

  Conventionally, water-based coating agents have been used in various fields and applications, and are required to have excellent toughness and light resistance. The acrylic resin water-based coating agent forms a film excellent in light resistance, gloss and alkali resistance, but problems have been pointed out in terms of bending resistance, impact resistance, abrasion resistance and the like. On the other hand, a polyurethane resin aqueous coating agent forms a tough film and is excellent in abrasion resistance, but has a problem in terms of light resistance and high price. Further, in recent years, there has been a demand for higher quality for coating films, and the demand for coating agents has been diversified and highly functional with the diversification of coating base materials and the development of new applications. In other words, in addition to light resistance, application to applications that require close contact with various substrates and that require toughness and wear resistance of the coating has been studied.

  Meeting these requirements is difficult to achieve with the conventional single material approach. For this reason, various proposals have recently been made regarding mixing or combining a plurality of materials having different characteristics. For example, a technique has been proposed in which a urethane copolymer aqueous dispersion having a hydrazino group is mixed with a ketonic carbonyl group-containing acrylic copolymer aqueous dispersion (for example, Patent Document 1 and Patent Document 2). Further, a resin composition has been proposed in which an aqueous polyurethane resin containing a ketonic carbonyl group is added to an acrylic copolymer having a ketonic carbonyl group, and a compound having a hydrazino group is further added as a crosslinking agent ( For example, Patent Document 3 and Patent Document 4).

However, in such a conventional resin composition, although it is said that drying, water resistance, coating film elasticity and the like can be achieved, a film having a sufficiently high degree of crosslinking cannot be formed, Sufficient results have not been obtained for these physical properties, particularly water resistance and solvent resistance. That is, since a ketonic carbonyl group can be introduced only into the molecular terminal of the urethane resin skeleton, the ketonic carbonyl group urethane resin alone can provide sufficient film elasticity and toughness, but has a low crosslinking density, so The solvent resistance could not be increased.
JP-A-1-301761 JP-A-1-301762 JP 7-11193 A JP-A-7-113061

  Therefore, in the present invention, although it is a water-based resin, it has excellent water resistance and solvent resistance, and has excellent performance as a binder for various coating agents such as adhesives, paints, and printing inks that have good adhesion to the plastic surface. An object of the present invention is to provide a one-component aqueous resin composition that is curable at room temperature and an aqueous coating composition using the same.

  The one-component aqueous resin composition of the present invention contains an organic polyisocyanate (a), a polyol compound (b) containing two or more active hydrogens having reactivity with an NCO group, and a ketonic carbonyl group. An aqueous system having two or more ketonic carbonyl groups in one molecule obtained by reacting with a carbonyl group-containing active hydrogen compound (c) containing two or more active hydrogens having reactivity with an NCO group A polyurethane-vinyl polymer composite (P) obtained by polymerizing a polymerizable unsaturated monomer (x) containing a polymerizable unsaturated monomer having a ketonic carbonyl group to polyurethane (A); And a hydrazide compound (e) having two or more hydrazino groups in the molecule.

  With this configuration, a ketonic carbonyl group is introduced into the polyurethane-vinyl polymer composite (P), and the ketonic carbonyl group is crosslinked by a compound having two or more hydrazino groups in one molecule of the component (e). Therefore, the obtained coating film is excellent in water resistance, solvent resistance and adhesiveness.

  The one-component aqueous resin composition of the present invention comprises an organic polyisocyanate (a), a polyol compound (b) containing two or more active hydrogens having reactivity with an NCO group, and a ketonic carbonyl group. Two or more ketonic carbonyl groups in one molecule obtained by polymerizing with a carbonyl group-containing active hydrogen compound (c) containing two or more active hydrogens that contain and have reactivity with NCO groups A polyurethane-vinyl polymer composite (Q) obtained by blending a water-based polyurethane (A) having a ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion (X) with two or more per molecule. And a hydrazide compound (e) having a hydrazino group.

  In this configuration, a ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion (X) is used in addition to the aqueous polyurethane (A) into which the ketonic carbonyl group has been introduced. The film is also excellent in water resistance, solvent resistance and adhesiveness.

  Furthermore, the one-component aqueous resin composition of the present invention comprises an organic polyisocyanate (a), a polyol compound (b) containing two or more active hydrogens having reactivity with an NCO group, and a ketonic carbonyl group. A polyurethane prepolymer (B) having an isocyanate group at the molecular end, obtained by polymerizing a carbonyl group-containing active hydrogen compound (c) containing at least two active hydrogens containing and reactive with NCO groups In contrast, two or more ketonic carbonyl groups and two hydrazide compounds (e) having two or more hydrazino groups in one molecule are obtained by reacting the molecular terminal free isocyanate group with two or more ketonic carbonyl groups and two in one molecule. A polymerizable unsaturated monomer comprising the above water-based polyurethane (C) having a hydrazino group and a polymerizable unsaturated monomer having a ketonic carbonyl group Polyurethane obtained by polymerizing a x) - characterized in that it contains a vinyl polymer composite (R).

  In this configuration, a ketonic carbonyl group is introduced into the polyurethane-vinyl polymer composite (R), and this ketonic carbonyl group reacts with a hydrazino group that is also introduced into the polyurethane-vinyl polymer composite (R). Therefore, the obtained coating film is excellent in water resistance, solvent resistance and adhesiveness.

  In addition, the one-part aqueous resin composition of the present invention comprises an organic polyisocyanate (a), a polyol compound (b) containing two or more active hydrogens having reactivity with an NCO group, and a ketonic carbonyl group. And a polyurethane prepolymer (B) having an isocyanate group at the molecular end obtained by polymerizing a carbonyl group-containing active hydrogen compound (c) containing at least two active hydrogens reactive with NCO groups On the other hand, two or more ketonic carbonyl groups and 2 in one molecule obtained by reacting the molecular terminal free isocyanate group with a hydrazide compound (e) having two or more hydrazino groups in one molecule. A water-based polyurethane (C) having at least one hydrazino group and a ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion (X) are blended. Resulting polyurethane - characterized by containing the vinyl polymer complex (S).

  In this configuration, the hydrazino group introduced into the polyurethane-vinyl polymer composite (S) is crosslinked by the ketonic carbonyl group introduced into the ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion (X). Therefore, the obtained coating film is excellent in water resistance, solvent resistance and adhesiveness.

  Here, the aqueous polyurethane (A) having two or more ketonic carbonyl groups in one molecule or the polyurethane prepolymer (B) having an isocyanate group at the molecular end further contains an ionic group having an ionic group. The compound (d) may be polymerized. By using the ionic group-containing compound (d), the dispersion stability of the obtained one-part aqueous resin composition can be improved.

  The carbonyl group-containing active hydrogen compound (c) containing the ketonic carbonyl group and containing two or more active hydrogens having reactivity with the NCO group is obtained by adding a dialkanolamine to diacetone acrylamide. It is preferable that it is a compound obtained. If this addition compound is used, a ketonic carbonyl group can be easily introduced into the water-based polyurethane (A) or polyurethane prepolymer (B).

  The hydrazide compound (e) having two or more hydrazino groups in one molecule is preferably adipic acid dihydrazide or an adipic acid dihydrazide derivative. By using adipic acid dihydrazide or an adipic acid dihydrazide derivative as a crosslinking agent, crosslinking can be performed by easily reacting with a ketonic carbonyl group in an aqueous polyurethane. Moreover, the water-based polyurethane (C) which introduce | transduced the hydrazino group into the terminal of a prepolymer can be easily obtained by making adipic acid dihydrazide or an adipic acid dihydrazide derivative react with a polyurethane prepolymer (B).

  In addition, as the hydrazide compound (e) having two or more hydrazino groups in one molecule, a molecule having two or more hydrazino groups in the molecule is reacted with a molecular terminal free isocyanate group, whereby a molecule A polyurethane prepolymer having a hydrazino group introduced at the terminal can also be used.

  Even with a polyurethane prepolymer having a hydrazino group introduced at the molecular end, crosslinking can be performed by easily reacting with a ketonic carbonyl group in an aqueous polyurethane.

  The aqueous coating composition of the present invention can be prepared using the one-component aqueous resin composition.

  The one-part aqueous resin composition of the present invention can not only freely introduce a ketonic carbonyl group into the molecule of the polyurethane-vinyl polymer composite, but also has a ketonic property on the molecular side chain of the polyurethane-vinyl polymer composite. Since a carbonyl group can be introduced, the crosslinking point with the dihydrazide compound (e) can be freely controlled. As a result, it is possible to obtain a urethane / acrylic composite film having a high degree of crosslinking, and it is possible to obtain sufficient film elasticity, toughness, water resistance, and solvent resistance as a room temperature curable resin while being a water-based resin. Become. Further, the one-component aqueous resin composition of the present invention can obtain a film excellent in water resistance and solvent resistance alone, and can obtain film elasticity and toughness equivalent to those of a solvent-based urethane resin. Become. In addition, the adhesion to the OPP and PET films subjected to corona discharge treatment is good, and the ink redissolvability in gravure printing is also good.

  As the organic polyisocyanate of component (a) used for the preparation of the one-component aqueous resin composition of the present invention, conventionally used aromatic, aliphatic or alicyclic organic polyisocyanates are used. Specific examples include aliphatic diisocyanates (eg, tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like), alicyclic diisocyanates (for example, isophorone diisocyanate, hydrogenated) Examples include silylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and the like, aromatic diisocyanates (for example, tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate , Xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc.), aroma Aliphatic diisocyanates (e.g., dialkyl diphenyl methane diisocyanate, tetraalkyl diphenylmethane diisocyanate, alpha, alpha, alpha, alpha-tetramethyl xylylene diisocyanate can be exemplified), tolylene diisocyanate - DOO and the like. These organic polysocyanates can be used alone or in a mixture of two or more.

  In addition, the polyol compound containing two or more active hydrogens having reactivity with the NCO group of the component (b) is a compound having a hydroxyl group, an amino group or a mercapto group, and is generally a known polyether, polyester, Polyetheresters, polythioethers, polyacetals, polybutadienes, polysiloxanes and the like. More preferable as the component (b) is a compound having two or more hydroxyl groups at the molecular terminals. Specifically, as the polyhydroxy compound having two or more active hydrogen groups as component (b), ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, diglycerin, pentaerythritol, sorbitol and other polyhydric alcohols, their oxyalkylene derivatives or their Obtained from polyhydric alcohol or oxyalkylene derivative and polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, or polycarboxylic acid ester Ester compound, a polycarbonate polyol, polycaprolactone polyol, polyester polyol, polythioether polyol, a polyacetal polyol, polytetramethylene glycol, polybutadiene polyol, castor oil polyol, fluorine polyol, a polyol compound or a modified product such as silicon polyols.

  (C) The carbonyl group-containing active hydrogen compound (c) containing a ketonic carbonyl group as a component and having two or more active hydrogens having reactivity with an NCO group is dialkanolamine with respect to diacetone acrylamide. What is obtained by addition reaction of can be illustrated.

Examples of the hydrazide compound having two or more hydrazino groups (—NHNH ₂ ) in one molecule of the component (e) used in the present invention include oxalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide. Succinic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide and the like, and dicarboxylic acid dihydrazides, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrantoin, carbohydrazide and the like. These may be used alone or in combination of two or more. Among these, adipic acid dihydrazide is more preferable from the viewpoint of versatility and good solubility in water. In addition, as the hydrazide compound of component (e), a polyurethane prepolymer in which a hydrazino group is introduced at the molecular end by reacting a hydrazide compound having two or more hydrazino groups in the molecule with respect to the molecular end free isocyanate group In this case, it is preferable to use adipic acid dihydrazide as the hydrazide compound having two or more hydrazino groups in one molecule.

  Examples of the polymerizable unsaturated monomer having a ketonic carbonyl group contained in the polymerizable unsaturated monomer (x) include diacetone acrylamide, acrolein, and vinyl methyl ketone.

  Furthermore, the ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion of the component (X) used in the present invention can be obtained by a general emulsion polymerization method or the like.

  In the present invention, an organic polyisocyanate (a), a polyol compound (b) containing two or more active hydrogens having reactivity with an NCO group, a ketonic carbonyl group and an NCO group An aqueous polyurethane (A) having two or more ketonic carbonyl groups in one molecule by reaction with a carbonyl group-containing active hydrogen compound (c) containing two or more reactive active hydrogens, or A polyurethane prepolymer (B) having an isocyanate group is obtained. The reaction conditions at that time are the same as in the case of preparation of an ordinary aqueous polyurethane or polyurethane prepolymer.

  In the present invention, the water-based polyurethane having two or more ketonic carbonyl groups and two or more hydrazino groups in one molecule of the component (C) is a polyurethane prepolymer having an isocyanate group at the molecular end. It can be obtained by reacting the molecular terminal free isocyanate group of B) with a hydrazide compound (e) having two or more hydrazino groups in one molecule. This reaction is performed by adding an aqueous solution of a hydrazide compound after dispersing the polyurethane prepolymer (B) in water.

  In preparing the water-based polyurethane (A) or urethane prepolymer (B), polymerization may be carried out in the presence of an ionic group-containing compound (d) having an ionic group. By copolymerizing the component (d), the dispersion stability of the resulting polyurethane-vinyl polymer composite can be improved.

  Examples of the ionic group-containing compound having an ionic group as component (d) include hydrophilic anionic properties such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and sodium dimethylisophthalate sulfonate. And cationic groups such as dimethylethanolamine and N-methyldiethanolamine.

    The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the present specification, “%” and “part” represent “% by weight” and “part by weight”, respectively, unless otherwise specified.

(Synthesis of ketonic carbonyl group-containing active hydrogen compound (c-1))
A diethanolamine adduct of diacetone acrylamide was synthesized as follows as a ketonic carbonyl group-containing active hydrogen compound of component (c).

  To 169 parts of diacetone acrylamide, 94.5 parts of diethanolamine was added and heated at 100 ° C. for 3 hours to obtain a ketonic carbonyl group-containing active hydrogen compound X. The bromine number of this ketonic carbonyl group-containing active hydrogen compound X was 6.1. The bromine number was measured according to JIS-K-3331.

<Synthesis of water-based polyurethane>
(Synthesis Example 1 ... Synthesis of water-based polyurethane (A-1))
300 parts of TESLAC 2460 (Hitachi Chemical Polymer Co., Ltd. polyester polyol: hydroxyl value 55), 107.2 parts of isophorone diisocyanate, and 114 parts of methyl ethyl ketone (MEK) were added and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 5.10 (%). Next, the temperature of the system was 50 ° C., 18.1 parts of dimethylolpropionic acid, 39.5 parts of ketonic carbonyl group-containing active hydrogen compound (c-1) synthesized above, 7.3 parts of triethylamine, methyl ethyl ketone 94.5 parts was added and reacted at 70-75 ° C. for 180 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.20 (%). After diluting this prepolymer with water under stirring, 5.8 parts of dipropylene triamine was added, the terminal NCO group was extended with an amine, and after confirming the disappearance of the free isocyanate group (%), methyl ethyl ketone was distilled off, An anionic aqueous polyurethane (A-1) having a ketonic carbonyl group in the molecular side chain of 30% pure was obtained. The theoretical carbonyl equivalent was 3490 (g / mol).

(Synthesis Example 2 ... Synthesis of water-based polyurethane (C-1))
300 parts, 107.2 parts of isophorone diisocyanate, and 139 parts of methyl ethyl ketone were added to Labe curve 106 (Polycarbonate polyol: hydroxyl value 55 manufactured by Mitex Co., Ltd.) and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 6.90 (%). Next, the temperature of the system was 50 ° C., 18.1 parts of dimethylolpropionic acid, 39.5 parts of ketonic carbonyl group-containing active hydrogen compound (c-1), 7.3 parts of triethylamine, 93.5 parts of methyl ethyl ketone Was added and reacted at 70-75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.20 (%). Under stirring, this prepolymer was diluted with dilute water in which 23.0 parts of adipic acid dihydrazide was dissolved. After confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone was distilled off to obtain a 30% pure molecular side. An anionic aqueous polyurethane (C-1) having a ketonic carbonyl group in the chain and a terminal hydrazino group was obtained. The theoretical carbonyl equivalent was 3640 g / mol.

(Synthesis Example 3 ... Synthesis of water-based polyurethane (A-2))
300 parts of TESLAC 2475 (Hitachi Chemical Polymer Co., Ltd. polyester polyol: hydroxyl value 55), 39.5 parts of ketonic carbonyl group-containing active hydrogen compound (c-1), 59.9 parts of isophorone diisocyanate, 206 parts of methyl ethyl ketone Were added and reacted at 70-75 ° C. for 90 minutes. The free isocyanate group content (in terms of solid content) at this time was 0.10 (%). Next, the temperature of the system was cooled to 50 ° C., 8.1 parts of acetic acid was added, and after sufficient stirring, this prepolymer was diluted with water under stirring, and after confirming disappearance of free isocyanate groups (%) Then, methyl ethyl ketone was distilled off to obtain a cationic aqueous polyurethane (A-2) having a ketonic carbonyl group in the molecular side chain having a pure content of 30%. The theoretical carbonyl equivalent was 2980 g / mol.

Synthesis Example 4 Synthesis of Hydrazide Compound (e-1)
300 parts of Teslac 2471 (polyester polyol manufactured by Hitachi Chemical Co., Ltd .: hydroxyl value 55), 83.3 parts of isophorone diisocyanate, and 114 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was set to 50 ° C., 20.1 parts of dimethylolpropionic acid, 1.5 parts of triethylamine, and 85.2 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer was cooled to 35 ° C., diluted water in which 26.8 parts of adipic acid dihydrazide was dissolved was added, and after confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone was distilled off to obtain a molecule with a pure content of 30%. An anionic hydrazide compound (e-1) having a hydrazino group at the end was obtained.

(Comparative Synthesis Example 1 ... Synthesis of water-based polyurethane (α))
300 parts of Teslac 2460 (Hitachi Chemical Polymer Co., Ltd. polyester polyol: hydroxyl value 55), 83.3 parts of isophorone diisocyanate, and 114 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was set to 50 ° C., 20.1 parts of dimethylolpropionic acid, 1.5 parts of triethylamine, and 85.2 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer was cooled to 60 ° C., 19.6 parts of diacetone alcohol was added, and reacted at 75 ° C. for 3 hours. At this time, the free isocyanate group was 0.2%. The prepolymer is cooled to 35 ° C., diluted water is added, and after confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone is distilled off, and an aqueous polyurethane having a ketonic carbonyl group only at the molecular terminal with a pure content of 30%. (Α) was obtained.

(Comparative Synthesis Example 2 ... Synthesis of water-based polyurethane (β))
300 parts of Teslac 2460 (Hitachi Chemical Polymer Co., Ltd. polyester polyol: hydroxyl value 55), 83.3 parts of isophorone diisocyanate, and 114 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 90 minutes. At this time, the free isocyanate group content (in terms of solid content) was 4.90 (%). Next, the temperature of the system was set to 50 ° C., 20.1 parts of dimethylolpropionic acid, 1.5 parts of triethylamine, and 85.2 parts of methyl ethyl ketone were added and reacted at 70 to 75 ° C. for 60 minutes. At this time, the free isocyanate group content (in terms of solid content) was 1.60 (%). The prepolymer is cooled to 35 ° C., diluted water is added, and an aqueous solution in which 6.7 parts of dipropylene triamine is dissolved is added. After confirming the disappearance of free isocyanate groups (%), methyl ethyl ketone is distilled off, A 30% aqueous polyurethane (β) was obtained.

<Production of polyurethane-vinyl polymer composite>
Using the raw materials shown in Table 1, composite emulsions of Examples and Comparative Examples were prepared as follows.

(Example 1 ... Preparation of one-part aqueous resin composition)
333 parts of the aqueous polyurethane (A-1) synthesized above, 233 parts of ion exchange water and 0.5 part of ammonium persulfate, 2 liters 4 equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer The mixture was charged into a three-necked flask and heated for 30 minutes from room temperature, and the temperature was raised to 80 ° C. while purging with nitrogen. From the dropping funnel, a mixture having the following composition was dropped over 2 hours. After completion of the dropping, the mixture was aged at 80 ° C. for 3 hours to carry out a graft polymerization reaction, thereby obtaining a polyurethane-vinyl polymer composite P-1. After cooling this complex P-1, 50.8 parts of 10% adipic acid dihydrazide aqueous solution was added to obtain a one-part aqueous resin composition of Example 1.

(Composition of dripping layer)
Butyl acrylate 20 parts Methyl methacrylate 50 parts Styrene 25 parts Diacetone acrylamide 5 parts.

<Examples 2 to 4 and Comparative Examples 1 and 2 ... Preparation of a one-part aqueous resin composition>
Similarly to the one-component aqueous resin composition of Example 1, the one-component aqueous resin compositions of Examples 2 to 4 and Comparative Examples 1 and 2 were prepared with the formulation shown in Table 1.

<Production of aqueous dispersion of vinylic monomer copolymer>
(Synthesis Example 5: Vinyl monomer copolymer aqueous dispersion (X-1))
233 parts of ion-exchanged water, 0.5 part of ammonium persulfate, 1.0 part of Haitenol NF-13 (Daiichi Kogyo Seiyaku Co., Ltd. anionic surfactant) were added to the reflux condenser, nitrogen inlet tube, thermometer, dropping funnel The mixture was charged into a 2 liter four-necked flask equipped with a stirrer and heated for 30 minutes from room temperature to 80 ° C. while purging with nitrogen. From the dropping funnel, a mixture having the following composition was dropped over 2 hours. After completion of the dropping, the mixture was aged at 80 ° C. for 3 hours to carry out a graft polymerization reaction, and a ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion. (X-1) was obtained.

(Composition of dripping layer)
Butyl acrylate 20 parts Methyl methacrylate 50 parts Styrene 25 parts Diacetone acrylamide 5 parts Hightenol NF-13 1 part.

(Synthesis Example 6 ... Vinyl monomer copolymer aqueous dispersion (γ))
233 parts of ion-exchanged water, 0.5 part of ammonium persulfate, 1.0 part of Haitenol NF-13 (Daiichi Kogyo Seiyaku Co., Ltd. anionic surfactant) were added to the reflux condenser, nitrogen inlet tube, thermometer, dropping funnel The mixture was charged into a 2 liter four-necked flask equipped with a stirrer and heated for 30 minutes from room temperature to 80 ° C. while purging with nitrogen. From the dropping funnel, a mixture having the following composition was dropped over 2 hours. After completion of the dropping, the mixture was aged at 80 ° C. for 3 hours to carry out a graft polymerization reaction, and a vinyl monomer copolymer water containing no ketonic carbonyl group. A dispersion (γ) was obtained.

(Composition of dripping layer)
Butyl acrylate 20 parts Methyl methacrylate 50 parts Styrene 30 parts Haitenol NF-13 1 part.

<Preparation of one-part aqueous resin composition: Examples 5 and 6 and Comparative Examples 3 to 7>
As shown in Table 2, the aqueous ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion prepared above was added to the aqueous polyurethanes prepared in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2. Further, a predetermined amount of 10% adipic acid dihydrazide aqueous solution was added to obtain one-component aqueous resin compositions of Examples 5 and 6 and Comparative Examples 3-7.

<Film coating test>
A one-component aqueous resin composition of each of the above examples and comparative examples was applied to (1) corona discharge treated biaxially stretched polyethylene terephthalate film and (2) corona discharge treated biaxially stretched polypropylene film (OPP). In 6), the film thickness after drying was 5 μm. Next, a sample for a coating test was prepared by drying for 48 hours in an environment of a temperature of 20 ° C. and a humidity of 65% RH. Using this sample, a cellophane tape peeling test, a water resistance test, and a solvent resistance test were conducted, and the evaluation results are shown in Tables 3 and 4. Each test method is as follows.

(Cellophane tape peel test (adhesion test))
A cross-cut peel test was performed. The remaining area of the coating film after the cellophane tape was peeled was measured. The evaluation criteria are as follows.

    A: The remaining film is 90% or more.

    B: Residual film is 50 to 90%.

    C: Residual film is less than 50%.

(Water resistance test)
Using a Gakushin type anti-friction tester, a cotton cloth soaked with water was attached to the arm part, and the water resistance was evaluated according to the following criteria from the state of the coated surface when rubbed 100 times with a load of 200 g.

    A: No change is observed on the coated surface.

    B: A streak is seen on the coated surface.

    C: The film is peeled over the entire coated surface.

(Solvent resistance test)
The coated surface was rubbed with a cotton swab soaked in ethyl alcohol, and the solvent resistance was evaluated according to the following criteria from the number of times (rubbed number) rubbed until the coated surface was dissolved in the solvent.

    A: Even if the number of rubbing times is 20, the coated surface does not dissolve.

    B: The coated surface dissolves when the number of rubbing is 5 to 20 times.

    C: The coated surface is dissolved when the number of rubbing is less than 5 times.

<Preparation of water-based ink: Examples 7 to 12 and Comparative Examples 8 to 13>
Emulsions, pigments, and solvents were mixed according to the formulations shown in Table 5 using the one-component aqueous resin compositions of the above Examples and Comparative Examples. 200 parts of 1 mmφ glass beads were blended with 200 parts of each mixed solution and dispersed with a sand grinder for 3 hours to make ink, and water-based inks of Examples 7 to 12 and Comparative Examples 8 to 13 were obtained. With respect to these water-based inks, IPA (isopropyl alcohol) re-dissolvability was evaluated, and samples in which these inks were applied to various films were prepared, and film adhesion, water resistance, and alcohol resistance were evaluated.

(Re-solubility test)
The aqueous ink obtained using the one-component aqueous resin composition of each of the above Examples and Comparative Examples was applied to a glass plate with a bar coater, dried for several seconds with a hand dryer, and then isopropyl alcohol / water = 8/2. The elution state of the coating film after being immersed for several seconds was visually observed and evaluated according to the following criteria. The evaluation results are shown in Tables 5 and 6.

    A: The coating film is completely dissolved by immersion twice or less.

    B: Half or more of the coating film dissolves by two immersions.

    C: The coating film does not dissolve even after two or more immersions.

(Preparation of coating sample on film)
Water-based inks obtained using the one-component water-based resin compositions of the above Examples and Comparative Examples were obtained from (1) corona discharge-treated biaxially stretched polyethylene terephthalate film, (2) corona discharge-treated biaxially stretched polypropylene film ( OPP) and (3) Corona discharge-treated nylon film was coated with a bar coater (# 6) so that the film thickness after drying was 5 μm. Then, it dried in the environment of temperature 20 degreeC and humidity 65% RH for 48 hours, and the application | coating sample to a film was created. Using these samples, a cellophane tape peeling test, a solvent resistance test and a water resistance test were conducted, and the evaluation results are shown in Tables 5 and 6. The test method and evaluation criteria are the same as described above.

<Preparation of aqueous coating agent ... Examples 13 to 18 and Comparative Examples 14 to 20>
The following formulations were prepared using the one-component aqueous resin compositions of the above Examples and Comparative Examples.

(Combination)
Ethylene glycol 9.0 parts Water 35.0 parts Primal 850 1.0 parts (Polycarboxylic acid type dispersant: Rohm and Haas)
28% ammonia water 1.0 part Neugen EA-157 1.0 part (nonionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd.)
Adecanol SX-568 3.0 parts (Antifoamer; Asahi Denka)
Tycop R-930 100.0 parts (Titanium oxide; Ishihara Sangyo Co., Ltd.)
Total (paint dispersion) 150.0 parts Next, the blend was dispersed with a disper for 40 minutes. Furthermore, the following formulation was added to obtain an aqueous coating agent.

(Composition of water-based paint)
Paint dispersion 150.0 parts Each resin emulsion 300.0 parts Texanol 15.0 parts (Eastman Chemical Japan Co., Ltd.)
Rheorate 216 (Appropriate amount added so that the viscosity is 10,000 to 100,000 mPa · s)
(Made by Elementis Japan).

<Performance evaluation>
About the water-based coating agent obtained above, coating viscosity, coating film gloss, coating film elongation, coating film strength, and accelerated light resistance were examined as described below. The results are shown in Tables 7 and 8.

(Viscosity of paint)
The paint viscosity (mPa · s) at 25 ° C. and 4 rpm was measured using a BH type viscometer.

(Paint gloss)
Each aqueous coating agent was applied to a glass plate with a 3 mil applicator, dried at room temperature for 3 days, and then the 60 ° reflectance (%) was measured according to JIS K 5660-1995.

(Evaluation of coating film elongation, coating film strength and accelerated light resistance according to JIS A6910)
A coating film was prepared so that the coating thickness after drying was 1 mm, and then cured according to the extension test method of JIS K6251-1993. The elongation percentage was measured using this test piece, and the coating strength at that time was determined. The accelerated light resistance was measured by observing the film elongation at 20 ° C. and −10 ° C. after irradiating a standard weather meter for 1000 hours with the same coating film as that measured for elongation.

  From the above, the one-component aqueous resin compositions of the above Examples and the water-based ink using the same were excellent in adhesion, water resistance and solvent resistance. On the other hand, the one-component aqueous resin composition of each comparative example and the water-based ink using the same were inferior in any of adhesiveness, water resistance or solvent resistance.

  In addition, each of the aqueous coating agents using the one-component aqueous resin composition of each of the above examples is excellent in terms of coating viscosity, coating gloss, coating elongation, coating strength, and accelerated light resistance. It was. On the other hand, the water-based coating agent using the one-component water-based resin composition of each comparative example has any of the following points: coating viscosity, coating film gloss, coating film elongation, coating film strength, or accelerated light resistance. It was inferior.

Since the one-component aqueous resin composition of the present invention can obtain a film of a polyurethane-vinyl polymer composite having a high degree of crosslinking, it can be used in the fields of binders for various coating agents such as adhesives, paints, and printing inks. Can be used.

Claims (10)

A polyol compound (b) containing at least two active hydrogens having reactivity with an organic polyisocyanate (a) and an NCO group; an active hydrogen having a ketonic carbonyl group and having reactivity with an NCO group; Aqueous polyurethane (A) having two or more ketonic carbonyl groups in one molecule obtained by reacting with two or more carbonyl group-containing active hydrogen compounds (c) has a ketonic carbonyl group. A polyurethane-vinyl polymer composite (P) obtained by polymerizing a polymerizable unsaturated monomer (x) containing a polymerizable unsaturated monomer;
A one-component aqueous resin composition comprising a hydrazide compound (e) having two or more hydrazino groups in one molecule. A polyol compound (b) containing at least two active hydrogens having reactivity with an organic polyisocyanate (a) and an NCO group; an active hydrogen having a ketonic carbonyl group and having reactivity with an NCO group; A water-based polyurethane (A) having two or more ketonic carbonyl groups in one molecule obtained by polymerizing two or more carbonyl group-containing active hydrogen compounds (c) is added to a ketonic carbonyl group-containing vinyl. Polyurethane-vinyl polymer composite (Q) obtained by blending water-soluble monomer copolymer aqueous dispersion (X),
A one-component aqueous resin composition comprising a hydrazide compound (e) having two or more hydrazino groups in one molecule. Polyol compound (b) containing two or more active hydrogens having reactivity with organic polyisocyanate (a) and NCO groups, 2 active hydrogens containing ketonic carbonyl groups and reactive with NCO groups The polyurethane prepolymer (B) having an isocyanate group at the molecular terminal obtained by polymerizing the carbonyl group-containing active hydrogen compound (c) containing at least one molecule, the molecular terminal free isocyanate group, An aqueous polyurethane (C) having two or more ketonic carbonyl groups and two or more hydrazino groups in one molecule, obtained by reacting a hydrazide compound (e) having two or more hydrazino groups with
A polyurethane-vinyl polymer composite (R) obtained by polymerizing a polymerizable unsaturated monomer (x) containing a polymerizable unsaturated monomer having a ketonic carbonyl group. A one-part aqueous resin composition. Polyol compound (b) containing two or more active hydrogens having reactivity with organic polyisocyanate (a) and NCO groups, 2 active hydrogens containing ketonic carbonyl groups and reactive with NCO groups The polyurethane prepolymer (B) having an isocyanate group at the molecular terminal obtained by polymerizing the carbonyl group-containing active hydrogen compound (c) containing at least one molecule, the molecular terminal free isocyanate group, An aqueous polyurethane (C) having two or more ketonic carbonyl groups and two or more hydrazino groups in one molecule, obtained by reacting a hydrazide compound (e) having two or more hydrazino groups with
One-part aqueous resin composition comprising a polyurethane-vinyl polymer composite (S) obtained by blending a ketonic carbonyl group-containing vinyl monomer copolymer aqueous dispersion (X) .   The aqueous polyurethane (A) having two or more ketonic carbonyl groups in one molecule is obtained by further polymerizing an ionic group-containing compound (d) having an ionic group. One-part aqueous resin composition.   The one-component aqueous resin composition according to claim 3 or 4, wherein the polyurethane prepolymer (B) having an isocyanate group at the molecular end is obtained by polymerizing an ionic group-containing compound (d) having an ionic group. Stuff.   The carbonyl group-containing active hydrogen compound (c) containing the ketonic carbonyl group and having two or more active hydrogens having reactivity with the NCO group is subjected to addition reaction of dialkanolamine with diacetone acrylamide. The one-component aqueous resin composition according to any one of claims 1 to 6, which is a compound obtained.   The one-component aqueous system according to any one of claims 1 to 7, wherein the hydrazide compound (e) having two or more hydrazino groups in one molecule is adipic acid dihydrazide or adipic acid dihydrazide derivative. Resin composition.   The hydrazide compound (e) having two or more hydrazino groups in one molecule reacts with a compound having two or more hydrazino groups in the molecule with respect to the molecular terminal free isocyanate group, thereby causing The one-component aqueous resin composition according to any one of claims 1 to 8, which is a polyurethane prepolymer having a hydrazino group introduced therein. An aqueous coating composition using the one-component aqueous resin composition according to claim 1.