JP6178900B2 - Aqueous resin composition - Google Patents

Description

  The present invention relates to a novel aqueous resin composition. More specifically, it forms a film with various properties such as excellent mechanical strength, water resistance, solvent resistance, heat resistance, durability, adhesion to the substrate, paint, surface treatment agent, coating agent, adhesion The present invention relates to an aqueous resin composition having storage stability that is not impaired over a long period of time and can be used in the field of agents, sealing agents and the like.

  In the technical field to which the present invention belongs, an aqueous resin composition containing an aqueous resin having a functional group capable of reacting with an oxazoline group and a polymer having an oxazoline group is disclosed (for example, see Patent Document 1). There is a disclosure of a water-soluble, water-dilutable or water-dispersible polymer having a functional group capable of reacting with an oxazoline group and a water-soluble polymer having an oxazoline group (see, for example, Patent Document 2). In the field of aqueous resin, a coating composition having antibacterial and antifungal properties by adding an antibacterial / antifungal agent to a polymer has been disclosed (for example, see Patent Document 3).

Japanese Patent Laid-Open No. 02-099537 JP 05-295275 A JP 2005-281299 A

  However, even in these technologies, when the aqueous resin composition is stored for a long period of time, the problem of maintaining the physical properties of the coating film, such as the appearance, water resistance, and solvent resistance of the coating film prepared using it, is solved. It has not reached. The subject of this invention is providing the aqueous resin composition which solves said problem by deterioration of the aqueous resin composition resulting from rot, and can show desired performance over a long period of time.

  In order to solve the above-mentioned problems, the present invention contains a polymer (A) having a carboxyl group as a main ingredient, and a water-soluble, water-dilutable or water-dispersible polymer (B) having a 2-oxazoline group as the above-mentioned The aqueous resin composition of the present invention is contained as a crosslinking agent for the polymer (A), and by adjusting the blending ratio of the polymers (A) and (B) and the blending ratio of the additive (C). The desired performance can be obtained over a long period of time that could not be achieved with conventional aqueous resin compositions.

Hereinafter, embodiments of the present invention will be described.
<About polymer (A)>
The polymer (A) used in the present invention is a polymer having a water-soluble, water-dilutable or water-dispersible carboxyl group. Examples of the polymer (A) having a carboxyl group include an acrylic resin, a polyester resin, a polyurethane resin, and a polyolefin resin, and an acrylic resin is preferable. When the main polymer (A) is an acrylic resin, the amount of the carboxyl group is preferably 100 parts by weight of the monomer mixture used as a raw material for the polymer (A) , preferably a monomer having a carboxyl group. By setting the amount to 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, and most preferably 3 to 8 parts by weight, the cured film of the aqueous resin composition of the present invention becomes tough, and water resistance, durability and substrate A film having excellent adhesion to the film is formed.

  In the polymer (A), examples of the monomer having a carboxyl group include monocarboxylic acids, dicarboxylic acids, and dicarboxylic acid monoesters. More specifically, (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, monomethyl itaconic acid, monobutyl itaconic acid, vinyl benzoic acid Oxalic acid monohydroxyethyl (meth) acrylate, carboxyl group-terminated caprolactone-modified acrylate (for example, “Placcel FA” series; manufactured by Daicel Industries), carboxyl group-terminal caprolactone-modified methacrylate (for example, “Placcel FMA” series; manufactured by Daicel Industries, Ltd.) And so on. Among these, (meth) acrylic acid and itaconic acid are preferable. One or more of these can be appropriately selected and used. Among these, (meth) acrylic acid that makes the viscosity as a polymer suitable for work is preferable.

  The monomer other than the monomer having a carboxyl group is not particularly limited. For example, the following can be exemplified, and one or more of them are appropriately selected in order to exert the performance derived from the monomer. Can be used.

  Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl acrylate, n-butyl methacrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl methacrylate , N-octyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl Alkyl of (meth) acrylic acid such as cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, etc. Le or cycloalkyl esters monomers.

  2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meta ) Hydroxyl group-containing monomers such as acrylates (for example, “Placcel F” series manufactured by Daicel Chemical Industries, etc.), particularly hydroxyl group-containing (meth) acrylic esters.

  Alkoxyalkyl esters of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane tripropoxy (meth) acrylate. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ- (meth) acryloyloxypropylhydroxy Hydroxysilanes such as silane and γ- (meth) acryloyloxypropylmethylhydroxysilane and / or hydrolyzable silane group-containing vinyl monomers.

  (Meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (Meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (methacrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, morpholine ethylene Oxide addition (meth) acrylate, N-vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrole, N-vinyl pyrrolidone, N-vinyl oxazolidone, N-vinyl sac N'imido, N- vinyl methyl carbamate, N, N- methyl vinyl acetamide, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, (meth) nitrogen-containing monomers such as acrylonitrile.

  Aziridinyl group-containing monomers such as (meth) acryloylaziridine and 2-aziridinylethyl (meth) acrylate.

  Glycidyl (meth) acrylate, α-methylglycidyl acrylate, α-methylglycidyl methacrylate (for example, “MGMA” manufactured by Daicel Chemical Industries), glycidyl allyl ether, oxocyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate (For example, “Cyclomer (registered trademark) A400” manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, “Cyclomer (registered trademark) M100” manufactured by Daicel Chemical Industries, Ltd.), etc. Group-containing monomers.

  Aromatic vinyl monomers such as α-methylstyrene, vinyltoluene and chloromethylstyrene.

  Acrolein, diacetone acrylamide, boromyrstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (such as vinyl ethyl ketone), (meth) acryloxyalkyl propenal, acetonyl acrylate, diacetone (meth) acrylate, 2- Carbonyl group-containing monomers such as hydroxypropyl acrylate acetyl acetate and butanediol-1,4-acrylate acetyl acetate. Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate.

4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine (for example, “Adekastab (registered trademark) LA-87” manufactured by Asahi Denka Kogyo), 4- (meth) acryloylamino-2,2, 6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine (for example, “Adekastab (registered trademark) LA-82” manufactured by Asahi Denka Kogyo), 4- (Meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) Acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidi 4- (meth) acryloyl amino -1,2,2,6,
6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine UV-stable monomers such as

2- [2'-Hydroxy-5 '-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (meth) acryloyloxyethylphenyl] -2H-1,2,3 -Benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -5-t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Aminomethyl-5′-t-octylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2′-hydroxy- 5 ′-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl Tyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro- 2H-benzotriazole, 2- [2′-hydroxy-5′-t-butyl-3 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2' -Hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-t-butyl-2H-benzotriazole, 2- [2'-H Proxy -5 '- (β- (meth) acryloyloxy ethoxy)-3'-t-butylphenyl] -4-t-butyl--2H- benzo benzotriazole ultraviolet absorbing monomers triazole and the like.

  2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] Such as ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-t-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone, etc. Benzophenone UV-absorbing monomers.

  The polymer (A) can be prepared by a known polymerization method such as ordinary solution polymerization or emulsion polymerization. When the polymer (A) main component is emulsion polymerization, the preferred molecular weight is preferably 100,000 to 3,000,000, more preferably 300,000 to 2,000,000, and most preferably 500,000 to 1,000,000 in terms of weight average molecular weight. By setting the molecular weight within this range, the balance between the film formability and durability of the coating film is improved.

  In water-soluble radical polymerization, the molecular weight is preferably 1000 to 50000, more preferably 3000 to 30000, and most preferably 5000 to 20000. By setting the molecular weight within this range, the balance between workability during coating and coating film durability is improved.

In the present invention, known polymers (A) can be widely used. For example, water-dispersible or water-soluble acrylic resin such as Acreset 19E, Acreset 210E, Acreset 260E, Acreset 288E, Allolon 453 (all manufactured by Nippon Shokubai Co., Ltd.); Sofranate AE-10, Sofranate AE-40 ( All are manufactured by Nippon Soflan Processing Co., Ltd.), Hydran HW-110, Hydran HW-131, Hydran HW-135, Hydran HW-320, Bondick 72070 (all manufactured by Dainippon Ink & Chemicals, Inc.), Poise 710, Poise Water dispersible polyurethane resins such as 720 (all manufactured by Kao Corporation), Mercy 525, Mercy 585, Mercy 414, Mercy 455 (all manufactured by Toyo Polymer Co., Ltd.); Bironal MD-1200, Bironal MD-1400, Water dispersible polyester resins such as Narl MD-1930 (all manufactured by Toyobo Co., Ltd.), WD3652 and WJL6342 (all manufactured by Eastman Chemical Co., Ltd.); Isoban-10, Isoban-06, Isoban-04 (all Kuraray isoprene) Chemical Co., Ltd.), Primacol 5981, Primacol 5983, Primacol 5990, Primacol 5991 (all manufactured by Dow Chemical Co., Ltd.) and the like, and water-soluble, water-dilutable or water-dispersible polyolefin resins, etc. it can.
<About polymer (B)>
The polymer (B) used as a crosslinking agent in the present invention is obtained by polymerizing an addition polymerizable oxazoline (a) and at least one other monomer (b) as required. In the present invention, the addition-polymerizable oxazoline (a) is represented by the following general formula (I).

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group or a substituted phenyl group, and R ₅ is an addition polymerizable unsaturated bond. Is an acyclic organic group having ]
Specific examples of the addition polymerizable oxazoline (a) include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl- 2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline can be mentioned, and one or a mixture of two or more selected from these groups can be used. Can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

The amount of addition polymerizable oxazoline (a) used is not particularly limited, but is preferably 5% by weight or more in the monomer mixture used for obtaining the polymer (B). If the amount is less than 5% by weight, the degree of curing is insufficient, and durability, water resistance and the like tend to be impaired. In the present invention, the other monomer (b) is not particularly limited as long as it is a monomer that does not react with the oxazoline group and is copolymerizable with the addition-polymerizable oxazoline (a). For example, (meth) acrylic acid Methyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and salts thereof (Meth) acrylic acid esters; unsaturated nitriles such as (meth) acrylonitrile; unsaturated compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, and N- (2-hydroxyethyl) (meth) acrylamide Amides; Vinyl esters such as vinyl acetate and vinyl propionate; Methyl vinyl ether, Ethyl vinyl Vinyl ethers such as ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; styrene, α-methylstyrene, styrenesulfonic acid Examples include α, β-unsaturated aromatic monomers such as sodium, and one or a mixture of two or more of these can be used.

  The polymer (B) is produced by polymerizing an addition polymerizable oxazoline (a) and, if necessary, at least one other monomer (b) in an aqueous medium by a conventionally known polymerization method. be able to. The aqueous medium that can be used is not particularly limited as long as it is miscible with water. For example, water; or water and methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, ethylene glycol , Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, acetone, methyl ethyl ketone and the like.

In order to impart water solubility to the polymer (B) as required, the ratio of the hydrophilic monomer in the monomer mixture used as the raw material for the polymer (B) is preferably 50% by weight or more, preferably 70% by weight or more. The hydrophilic monomer means addition-polymerizable oxazoline (a) and other monomers (b), 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) Examples include 2-aminoethyl acrylate and salts thereof, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrenesulfonate, and the like. It can also be prepared by emulsion polymerization.

  In the present invention, the blending ratio of the polymer (A) and the polymer (B) is preferably in the range of 1 to 50 parts by weight of the polymer (B) with respect to 100 parts by weight of the polymer (A). A range of 3 to 10 parts by weight is more preferable, and a range of 3 parts by weight is more preferable. By setting the amount ratio within this range, the degree of curing is sufficient, durability, water resistance, etc. are good, and adhesion to the substrate is good.

  The composition of the present invention may contain a solvent, a plasticizer, an inorganic or organic filler, a color pigment, a dye, a thickener, a dispersant, a wetting agent, an antifoaming agent, as necessary, as long as the object of the present invention is not impaired. It is also possible to add an agent, a rust inhibitor and the like. When producing the composition of the present invention, it is not particularly limited, and means commonly used by those skilled in the art can be widely applied. For example, the polymer (B) can be applied to an aqueous solution, water dilution or water dispersion of the polymer (A). ) And other additives may be added and mixed as necessary. And when using for a coating material, a surface treating agent, a coating agent, an adhesive agent, and a sealing agent, what is necessary is just to apply | coat to a base material by the said traders' usual methods, such as a roll coater, spray, immersion, and brush coating. Curing can be performed at room temperature for 1 day to 2 weeks, but if necessary, it can also be performed by heating at 120 ° C. for about 30 minutes.

<About additive (C)>
Additive C suppresses the generation of organisms (mold, bacteria, plankton, etc.) often generated in the aqueous resin composition and maintains the performance of the coating film derived from the aqueous resin composition. Additive (C) is Cosmocil CQ (produced by AVECIA, active ingredient 20%), Actiside MB (produced by So Japan Co., Ltd., active ingredient 5%), Fineside HS-10 (produced by Tokyo Fine Chemical Co., Ltd., active ingredient 5%) PERMACHEM Topside-1000 (manufactured by Permachem Asia, active ingredient 5%) and the like are preferably used, and chlorine-based Cosmocil CQ and Topside 1000 are particularly preferably used from the viewpoint of suppressing the generation of organisms.

  The use amount of the additive (C) is preferably 0.0001 to 0.01 part by weight as an active ingredient with respect to 1 part by weight of the polymer (B). More preferably, it is 0.00015-0.005 weight part, More preferably, it is 0.00018-0.003 weight part.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example.
In the following, “%” represents “% by weight” and “parts” represents “parts by weight” unless otherwise specified.

<Production Example 1 (Production Example of Polymer (A) Acrylic Emulsion)>
In a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer and dropping funnel, 376.5 parts deionized water and Haitenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd. polyoxyethylene nonylphenyl ether ammonium sulfate) Salt) 70.8 parts of a 15% aqueous solution was charged and heated to 80 ° C. while gently flowing nitrogen gas. 5% of a monomer mixture consisting of 131 parts of 2-ethylhexyl acrylate, 205 parts of styrene and 17 parts of acrylic acid prepared in advance was charged into a flask, and then 21 parts of a 5% aqueous solution of potassium persulfate was injected. Polymerization was started. After 10 minutes, the remaining monomer mixture was added dropwise over 3 hours. Nitrogen gas was continuously blown during the reaction, and the temperature in the flask was kept at 80 ± 1 ° C. After maintaining the same temperature for 1 hour after the completion of dropping, the mixture was cooled and adjusted to pH 8.5 with 9 parts of 25% aqueous ammonia to obtain an acrylic emulsion (3) having a nonvolatile content of 44.1% and a pH of 8.5.

<Production Example 2 (Production Example of Polymer (B) Water-soluble Resin)>
A flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer was charged with 1350 parts of deionized water, 5 parts of sodium persulfate, 120 parts of 2-isopropenyl-2-oxazoline and 30 parts of ethyl acrylate, and gently The mixture was heated to 50 ° C. while flowing nitrogen gas. The temperature in the flask was kept at 50 ± 1 ° C. and stirring was continued for 10 hours to complete the reaction, followed by cooling, and 0.15 part of Cosmocil CQ was added. An oxazoline group-containing polymer aqueous solution (1) having a nonvolatile content of 10.2% was obtained. The number average molecular weight of this polymer was about 20,000.

<Production Example 3 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2, except that 1.5 parts of Cosmocil CQ of Production Example 2 was added.

<Production Example 4 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2, except that Cosmocil CQ of Production Example 2 was changed to 0.6 part PERMACHEM Topside-1000.

<Production Example 5 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2, except that CosmocilCQ in Production Example 2 was changed to 0.6 parts of Actiside MB.

<Production Example 6 (Production Example of Polymer (B) Water-soluble Resin)>
Production Example 2 except that CosmocilCQ in Production Example 2 was changed to 0.6 part of Fine Side HS-10
the same as.

<Production Example 7 (Production Example of Polymer (B) Emulsion)>
In a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer and dropping funnel, 782.4 parts of deionized water and Haitenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd. polyoxyethylene nonylphenyl ether ammonium sulfate) Salt) 128 parts of a 15% aqueous solution was charged, adjusted to pH 9.0 with an appropriate amount of 28% aqueous ammonia, and heated to 70 ° C. while gently flowing nitrogen gas. Thereto, 64 parts of a 5% aqueous solution of potassium persulfate was injected, and then a monomer mixture consisting of 288 parts of butyl acrylate, 288 parts of styrene and 64 parts of 2-isopropenyl-2-oxazoline prepared in advance was prepared. Added dropwise over 3 hours. Nitrogen gas was continuously blown during the reaction, and the temperature in the flask was kept at 70 ± 1 ° C. After the completion of the dropwise addition, the same temperature was maintained for 2 hours, and then the internal temperature was raised to 80 ° C. and stirring was continued for 1 hour to complete the reaction. Thereafter, the mixture was cooled, and 0.64 part of Cosmosil CQ was added. An aqueous oxazoline group-containing polymer dispersion (3) having a nonvolatile content of 39.8% and a pH of 8.0 was obtained.

<Production Example 8 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2, except that 15.0 parts of Cosmocil CQ of Production Example 2 was added.

<Production Example 9 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2 except that CosmocilCQ of Production Example 2 is not added.

<Production Example 10 (Production Example of Polymer (B) Water-soluble Resin)>
Same as Production Example 2 except that CosmocilCQ of Production Example 7 is not added.
The results are shown in Table 1.

[Septic resistance test]
Samples of each Example and Comparative Example having the composition shown in Table 1 are placed in a 110 ml sample bottle, sealed, and stored at 30 ° C. for 180 days in the dark. After 180 days, change is visually confirmed. The evaluation was visually evaluated as ◯ if there was no change from the beginning, Δ if a slight mold was generated, and x if a lot of mold was generated.
Examples 4 to 6 are treated as reference examples (the same applies hereinafter).

[Water whitening test]
Table 1 mixture of real施例1-6 and Comparative Examples 1 to 3 was blended with was made adjustment, after 180 days, the CS-12 of the film forming aid (manufactured by Chisso) to the solid to the respective mixture and stand for 24 hours was added by 8 parts for. Using this applicator, the dry film thickness is 150 μm on a glass plate (length: 15 cm, width: 7 cm) in an atmosphere having a temperature of 23 ± 2 ° C. and a relative humidity of 65 ± 3%. The glass plate was coated, left in this atmosphere for 2 minutes, then heated at 120 ° C. for 30 minutes, and then allowed to cool to produce a glass plate on which a coating film was formed. After a glass tube having a diameter of 30 mm and a length of 30 mm was adhered to the coating film of the glass plate on which this coating film was formed, 10 mL of ion exchange water was poured into the glass tube, and the temperature was 23 ± 2 ° C. After leaving in an atmosphere having a relative humidity of 65 ± 3% for 24 hours, the state of the coating film in contact with ion-exchanged water was visually observed and evaluated based on the following evaluation criteria. In addition, compared with the coating film before the test start, the crosslinking performance is so good that there is no change in the coating film after the test.
(Evaluation criteria)
○: No change is observed in the coating film.
Δ: Some cloudiness is observed in a part of the coating film.
X: The whole coating film is whitened.

[Solvent resistance test: MEK rubbing test]
After conducting a rubbing test in which the coating film of the glass plate on which the coating film obtained above was formed was rubbed 50 times with absorbent cotton containing MEK, the state of the coating film was visually observed, and the following evaluation criteria Based on the evaluation. The crosslinkability is so good that there is no change in the coating film.
(Evaluation criteria)
○: No change is observed in the coating film.
(Triangle | delta): Dissolution is recognized by a part of coating film.
X: Dissolution is observed in the entire coating film.

[Film appearance test]
The state of the coating film was observed after leaving the coating film of the glass plate in which the coating film obtained above was formed in a constant temperature and humidity machine of 30 ° C. × 80% RH for 30 days.
(Evaluation criteria)
○: No change is observed in the coating film.
Δ: Some whitening is observed in a part of the coating film.
X: The whole coating film is whitened.

  The aqueous resin composition of the present invention forms a film having various properties such as excellent mechanical strength, water resistance, solvent resistance, heat resistance, durability, adhesion to a substrate, paint, surface treatment agent , Coating agents, adhesives, sealing agents and the like.

Claims (3)

A polymer (A) having a carboxyl group, a polymer (B) having a 2-oxazoline group, and an additive (C), and having a 2-oxazoline group with respect to 100 parts by weight of the polymer (A) having a carboxyl group The amount of the polymer (B) is 1 to 50 parts by weight, and the amount of the additive (C) with respect to 1 part by weight of the polymer (B) having a 2-oxazoline group is 0.0001 to 0.01 parts by weight. The monomer mixture used as a raw material for the polymer (B) having a 2-oxazoline group is a monomer mixture containing 50% by weight or more of a hydrophilic monomer, and addition polymerization is performed as the hydrophilic monomer. A water-based paint characterized in that a functional oxazoline (a) is used and the additive (C) is a preservative containing chlorine. The polymer (A) having a carboxyl group is an acrylic resin obtained by polymerizing a monomer mixture comprising 1 to 15 parts by weight of a monomer having a carboxyl group and 85 to 99 parts by weight of another monomer. Water-based paint. Aqueous paint according to Ru claim 1 or 2 Na with polyhexamethylene biguanide hydrochloride or isothiazolone chloride is used as a preservative containing chlorine.