JP5248809B2 - Water-based resin composition and water-based coating composition - Google Patents

Description

The present invention relates to an aqueous resin composition capable of imparting hydrophilicity to a substrate by blending in a paint and improving the stain resistance, an aqueous paint composition containing the aqueous resin composition, and a method for forming a coating film. About.

Organic solvent-type paints have been conventionally used because paints applied to building exteriors and steel structures used outdoors are required to have long-term durability. In recent years, water-based paints are increasingly used for the purpose of reducing environmental burdens caused by VOCs and reducing the burden on painters.

  When a water-based paint is applied to the above-mentioned building exterior or the like, contamination resistance is particularly problematic. As a technique for imparting stain resistance to a coating film obtained by applying a paint, a technique for keeping the coating film hydrophilic is known.

  Patent Document 1 relates to a coating composition, and includes a fluoroolefin polymer, fluorine (meth) acrylate, a hydrophilic structural unit-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers. A coating composition comprising a copolymer obtained by polymerizing a polymer, a compound having a hydrolyzable silyl group as an essential component, and a monomer polymer containing a (meth) acryloyl group is disclosed. Has been.

  In the technique disclosed in Patent Document 1, a fluoroolefin polymer, fluorine (meth) acrylate, a hydrophilic structural unit-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers are polymerized. The resulting copolymer is coated with a perfluoroalkyl group and a hydrophilic structural unit so that hydrophilicity is expressed on the surface of the coating film, and silanol groups produced by hydrolysis of silyl groups in the coating film are present. There exists an effect | action which improves the hydrophilic property of a coating film. However, when applied to water-based paints, the condensation of silanol groups generated by reaction with water in the paints occurs, and there is a concern about storage thickening of the paints.

  On the other hand, even if the coating film is made hydrophilic by simply adding a hydrophilic substance to the water-based paint, it is easily washed away by rain or the like, and it is difficult to maintain the effect of stain resistance for a long time.

JP 10-36754 A

An object of the present invention is to provide an aqueous resin composition that can be applied to a water-based paint, and that a coating film obtained by applying the water-based paint exhibits hydrophilicity at an early stage and that the effect continues for a long period of time. It is.

As a result of earnestly examining the above-mentioned problems, the present inventors have found that a fluorine-containing polymerizable unsaturated monomer, an acid group-containing polymerizable unsaturated monomer, a hydrophilic group-containing polymerizable unsaturated monomer, a functional group other than an acid group and a hydrophilic group. A fluorine-containing resin composition containing a polymerizable unsaturated monomer having a group and, if necessary, another polymerizable unsaturated monomer as a copolymerization component, can be dissolved and dispersed in water.
It has good compatibility with the aqueous resin used as a binder, and the aqueous resin composition containing the fluorine-containing resin composition and other aqueous binder resins expresses hydrophilicity from an early stage and is maintained for a long period of time. And reached the present invention.
That is, the present invention
1. Fluorine-containing polymerizable unsaturated monomer (a), acid group-containing polymerizable unsaturated monomer (b), hydrophilic group-containing polymerizable unsaturated monomer selected from hydroxyl group, alkoxypolyoxyalkylene group, amide group and morpholino group ( c), a fluorine-containing aqueous resin composition obtained by copolymerizing a polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group and, if necessary, another polymerizable unsaturated monomer (e). An aqueous resin composition comprising (I) and an aqueous binder resin (II) other than (I) having a reactive group with a polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group And the functional group other than the acid group and the hydrophilic group in the polymerizable unsaturated monomer (d) having a functional group other than the acid group and the hydrophilic group of the fluorine-containing aqueous resin composition (I) is an epoxy group, Isocyan Over preparative group, the amount of isocyanate groups protected with alcohol or oxime, carbonyl group, radically polymerizable and fluorine-containing aqueous resin composition I der those selected from the group having an unsaturated bond (I) is An aqueous resin composition having a solid content of more than 0 and less than 15% by mass with respect to the aqueous binder resin (II) ,
2. A group or ketone having a carbon-carbon double bond derived from an unsaturated fatty acid in which the functional group of the polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group is a radical polymerizable unsaturated bond 2. The aqueous resin composition according to 1, which is at least one group selected from the group consisting of hydrophilic carbonyl groups,
3. Fluorine-containing aqueous resin composition (I) is a fluorine-containing polymerizable unsaturated monomer (a) 1 to 5
0% by mass, acid group-containing polymerizable unsaturated monomer (b) 1 to 90% by mass, hydrophilic group-containing polymerizable monomer
Saturated monomer (c) 1 to 90% by mass, polymerizable unsaturated having functional group other than acid group and hydrophilic group
Sum monomer (d) 1-50 mass% and other polymerizable unsaturated monomer (e) 0-60 mass
The aqueous resin composition according to item 1 or 2, which is a copolymer of a monomer mixture comprising
4). The present invention relates to an aqueous coating composition comprising the aqueous resin composition according to any one of items 1 to 3 .

When the aqueous resin composition of the present invention is blended with an aqueous paint, the fluorine-containing aqueous resin composition contained in the aqueous resin composition migrates to the surface due to the effect of fluorine when a coating film is formed with the aqueous paint. The surface layer of the coating film is hydrophilized by the effect of the hydrophilic group in the aqueous resin composition, and the coating film having excellent stain resistance can be formed. Furthermore, the outflow of hydrophilic components from the surface of the coating film is suppressed by the individual crosslinking of the functional group contained in the fluorine-containing aqueous resin composition and / or the mutual crosslinking with the binder resin and the crosslinking agent in the aqueous coating material, and the coating film surface layer The effect of hydrophilizing lasts for a long time.

The fluorine-containing polymerizable unsaturated monomer (a) used in the aqueous resin composition of the present invention is a fluorine-containing aqueous solution of the present invention in a coating film obtained by applying an aqueous paint containing the aqueous resin composition of the present invention. It is used to orient the resin composition (I) on the surface and is a compound having fluorine and a polymerizable unsaturated group in the molecule. In the present specification, the polymerizable unsaturated group means a radically polymerizable carbon-carbon double bond such as a vinyl group, an allyl group, a styryl group, or a (meth) acryloyl group.

  Specific examples of fluorine-containing polymerizable unsaturated monomers include fluorine-containing vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, etc. -Α-olefin; perfluoroalkyl trifluorovinyl ether such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, heptafluoropropyl trifluorovinyl ether, and (per) fluoroalkyl vinyl ether; Mention may be made of fluoroalkyl group-containing (meth) acrylates.

R in the above formula is a hydrogen atom or a methyl group, X is hydrogen, chlorine, bromine, a hydrocarbon group or fluoroalkyl group that may be branched, m is an integer of 0 to 5, and n is 1 Is an integer of -12, a is an integer of 1 or more, b is an integer of 0 or more, and a + b satisfies 2n + 1.

_{Examples, CH 2 = CHCO 2 C 2} F 5, CH 2 = CHCO 2 CH 2 C 3 F 7, CH 2 = CHCO 2 CH 2 C 4 F 9, CH 2 = CHCO 2 CH 2 C 5 F 11 _{, CH 2 = CHCO 2 CH 2} C 6 F 13, CH 2 = CHCO 2 CH 2 C 7 F 15, CH 2 = CHCO 2 CH 2 C 8 F 17, CH 2 = CHCO 2 CH 2 C 9 F 19, CH _{2 = CHCO 2 CH 2 C 10} F 21, CH 2 = CHCO 2 CH 2 C 11 F 23, CH 2 = CHCO 2 CH 2 C 12 F 25, CH 2 = C (CH 3) CO 2 CH 2 C 2 F _{5, CH 2 = C (CH} 3) CO 2 CH 2 C 3 F 7, CH 2 = C (CH 3) CO 2 CH 2 C 4 F 9, CH 2 = C (CH 3) CO 2 CH 2 _{5 F 11, CH 2 = C} (CH 3) CO 2 CH 2 C 6 F 13, CH 2 = C (CH 3) CO 2 CH 2 C 7 F 15, CH 2 = C (CH 3) CO 2 CH 2 _{C 8 F 17, CH 2 =} C (CH 3) CO 2 CH 2 C 9 F 19, CH 2 = C (CH 3) CO 2 CH 2 C 10 F 21, CH 2 = C (CH 3) CO 2 CH _{2 C 11 F 23, CH 2} = C (CH 3) CO 2 CH 2 C 12 F 25, CH 2 = CHCO 2 C 2 H 4 C 2 F 5, CH 2 = CHCO 2 C 2 H 4 C 3 F 7 _{, CH 2 = CHCO 2 C 2} H 4 C 4 F 9, CH 2 = CHCO 2 C 2 H 4 C 5 F 11, CH 2 = CHCO 2 C 2 H 4 C 6 F 13, CH 2 = CHCO 2 C 2 H ₄ C ₇ F ₁₅ , CH ₂ ═CH _{CO 2 C 2 H 4 C 8} F 17, CH 2 = CHCO 2 C 2 H 4 C 9 F 19, CH 2 = CHCO 2 C 2 H 4 C 10 F 21, CH 2 = CHCO 2 C 2 H 4 C 11 _{F 23, CH 2 = CHCO 2} C 2 H 4 C 12 F 25, CH 2 = C (CH 3) CO 2 C 2 H 4 C 2 F 5, CH 2 = C (CH 3) CO 2 C 2 H 4 _{C 3 F 7, CH 2 =} C (CH 3) CO 2 C 2 H 4 C 4 F 9, CH 2 = C (CH 3) CO 2 C 2 H 4 C 5 F 11, CH 2 = C (CH 3 _{) CO 2 C 2 H 4 C} 6 F 13, CH 2 = C (CH 3) CO 2 C 2 H 4 C 7 F 15, CH 2 = C (CH 3) CO 2 C 2 H 4 C 8 F 17, _{CH 2 = C (CH 3)} CO 2 C 2 H 4 C 9 F 19, CH 2 _{= C (CH 3) CO 2} C 2 H 4 C 10 F 21, CH 2 = C (CH 3) CO 2 C 2 H 4 C 11 F 23, CH 2 = C (CH 3) CO 2 C 2 H 4 _{C 12 F 25, CH 2 =} C (CH 3) CO 2 CH 2 CF 2 CHF 2, CH 2 = C (CH 3) CO 2 C 2 H 4 CF (CF 3) 2 and the like can be exemplified, 1 Species or two or more types can be used in combination.

  Fluorine-containing polymerizable unsaturated monomer (a) The number of fluorine atoms in one molecule depends on the acid group-containing polymerizable unsaturated monomer (b), hydrophilic group-containing polymerizable unsaturated monomer (c) and crosslinkable functional group described later. In view of compatibility with the polymerizable unsaturated monomer (d) having a group, it is preferably in the range of 5 to 17, and in particular, other polymerizable unsaturated monomers in which the polymerizable unsaturated monomer having 9 fluorine atoms is copolymerized. It is preferable because of its excellent compatibility with saturated monomers and stability in water-based paints.

  In the fluorine-containing aqueous resin composition (I) of the present invention, the acid group-containing polymerizable unsaturated monomer (b) is water-soluble or water-dispersible when the aqueous resin composition of the present invention is applied as an aqueous paint. To improve the compatibility with the aqueous binder resin (II). Specific examples include (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, isocrotonic acid, α-ethylacrylic acid, β-ethylacrylic acid, β-propylacrylic acid, β-isopropylacrylic acid, β-carboxyl Carboxyl group-containing polymerizable unsaturated monomers such as ethyl acrylate; Phosphoric acid group-containing polymerizable unsaturated monomers such as mono (acryloyloxyethyl) acid phosphate and mono (methacryloyloxyethyl) acid phosphate; p-vinylbenzenesulfonic acid And sulfonic acid group-containing polymerizable unsaturated monomers such as p-acrylamide propane sulfonic acid and t-butyl amide propane sulfonic acid, can be used alone or in combination of two or more.

  In the fluorine-containing aqueous resin composition (I) in the present invention, the hydrophilic group-containing polymerizable unsaturated monomer (c) is applied to the aqueous paint when the aqueous resin composition of the present invention is applied as an aqueous paint. This is a compound having an effect of hydrophilizing the surface of the coating film obtained and having a hydrophilic group other than an acid group and a polymerizable unsaturated group in the molecule. Specific examples of the hydrophilic group include a hydroxyl group, an alkoxypolyoxyalkylene group, an amide group, and a morpholino group.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate ( meth) _C 2 -C ₈ hydroxyalkyl esters of acrylic acid, allyl alcohol, having a hydroxyl group such as ε- caprolactone modified products of the above _C 2 -C ₈ hydroxyalkyl (meth) acrylate (meth) acrylate; molecular end with hydroxyl groups (Meth) acrylate having a polyoxyethylene chain; allyl alcohol, trimethylolpropane monoallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, poly Ethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl Examples include hydroxyl group-containing allyl compounds such as ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, pentaerythritol triallyl ether, and the like. Can be used in combination.

  Examples of the alkoxy polyoxyalkylene group-containing polymerizable unsaturated monomer include compounds that can be represented by the following formula.

R in the above formula is a hydrogen atom or a methyl group, R ¹ is an alkyl group having 1 to 24 carbon atoms, p is an integer of 2 or 3, and q is an integer of 2 to 200.

  Examples of the amide group-containing polymerizable unsaturated monomer include N-alkylacrylamide, N, N-dialkylacrylamide, acrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide, and methacrylamide.

  Examples of the morpholino group-containing polymerizable unsaturated monomer include (meth) acryloylmorpholine.

  Furthermore, the polymerizable unsaturated monomer which has a hydroxyl group and an amide group simultaneously, such as N-methylol acrylamide and hydroxyethyl acrylamide, is also mentioned.

  The polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group, used in the fluorine-containing aqueous resin composition (I) in the present invention, is transferred to the surface by the effect of fluorine. The aqueous resin composition (I) is fixed by cross-linking to suppress water loss. Examples of crosslinking include single crosslinking of the fluorine-containing aqueous resin composition (I), mutual crosslinking with an aqueous binder-resin component (II) or a crosslinking agent, and the like. If it forms, it will not specifically limit. Specific functional groups other than acid groups and hydrophilic groups include epoxy groups, isocyanate groups, isocyanate groups protected with alcohols, oximes, etc., carbonyl groups, carbon-carbon double bonds derived from oxidatively polymerizable fatty acids, and radicals. Examples thereof include a group having a polymerizable unsaturated bond, and these can be used alone or in combination of two or more.

  Among the polymerizable unsaturated monomers having a functional group other than the acid group and the hydrophilic group described above, a ketonic carbonyl group is used for incorporation into a carbonyl-hydrazide bridge used as a crosslinking system for a room temperature-curable aqueous coating. It is preferable to use a polymerizable unsaturated monomer. In addition, if a polymerizable unsaturated monomer having a carbon-carbon double bond derived from an oxidatively polymerizable fatty acid is used, crosslinking can be performed only with the fluorine-containing aqueous resin composition (I) regardless of the type of the aqueous binder (II) to be combined. Since it can be formed, the application range is wide and suitable.

  Examples of the polymerizable unsaturated monomer having a ketonic carbonyl group include diacetone (meth) acrylamide and acetoacetoxyethyl (meth) acrylate.

  As the polymerizable unsaturated monomer having a carbon-carbon double bond derived from an oxidatively polymerizable fatty acid, fatty acid modification obtained by reacting a fatty acid with an epoxy group-containing polymerizable unsaturated monomer or a hydroxyl group-containing polymerizable unsaturated monomer Listed are polymerizable unsaturated monomers.

  Examples of the fatty acid include those having a structure in which a carboxyl group is bonded to the end of the hydrocarbon chain, and examples thereof include dry oil fatty acid, semi-dry oil fatty acid, and non-dry oil fatty acid. Dry oil fatty acids and semi-dry oil fatty acids cannot be strictly distinguished, but usually dry oil fatty acids are unsaturated fatty acids having an iodine value of 130 or more, and semi-dry oil fatty acids have an iodine value of 100 or more and less than 130. Of unsaturated fatty acids. On the other hand, non-drying oil fatty acids are usually fatty acids having an iodine value of less than 100.

  Examples of the dry oil fatty acid and semi-dry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape Nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hydienoic acid fatty acid, etc., and non-drying oil fatty acid include, for example, coconut oil fatty acid , Hydrogenated coconut oil fatty acid, palm oil fatty acid and the like. These can be used alone or in combination of two or more. Furthermore, these fatty acids can be used in combination with caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like.

  Examples of the epoxy group-containing polymerizable unsaturated monomer to be reacted with the fatty acid include compounds having one or more epoxy groups and one polymerizable unsaturated group in one molecule. Specifically, for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxy Examples thereof include cyclohexylpropyl (meth) acrylate and allyl glycidyl ether. These can be used alone or in combination of two or more.

  The fatty acid and the epoxy group-containing polymerizable unsaturated monomer have an equivalent ratio of a carboxyl group in the fatty acid and an epoxy group in the epoxy group-containing monomer of 0.75: 1 to 1.25: 1, preferably 0.8: The reaction can be carried out at such a ratio that it is within the range of 1 to 1.2: 1.

  The reaction of the above fatty acid with an epoxy group-containing polymerizable unsaturated monomer is usually carried out in the presence of a polymerization inhibitor without causing a problem in the reaction such as gelation and the carboxyl group and epoxy group-containing polymerization in the fatty acid component. The reaction can be carried out under conditions that allow the epoxy group in the unsaturated monomer to react smoothly, and it is usually preferable to carry out the heating at a temperature of about 100 to about 180 ° C. for about 0.5 to about 10 hours. In this reaction, an esterification reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used. And inert organic solvents can be used.

  Examples of the polymerization inhibitor include phenolic hydroxyl group-containing compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2 Nitro compounds such as 1,4-dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone and phenanthroquinone; nitrosobenzene and nitroso-β- Examples thereof include known radical polymerization inhibitors such as nitroso compounds such as naphthol, and these can be used alone or in combination of two or more.

  The fatty acid-modified polymerizable unsaturated monomer can also be obtained by esterifying the fatty acid with a hydroxyl group-containing polymerizable unsaturated monomer. Such hydroxyl group-containing polymerizable unsaturated monomers include compounds having one or more hydroxyl groups and one polymerizable unsaturated group in one molecule. Specifically, for example, 2-hydroxyethyl (meth) acrylate. -C2-C8 hydroxyalkyl (meth) acrylate of (meth) acrylic acid such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol , (Meth) acrylate having a hydroxyl group such as a modified ε-caprolactone of the above C2-C8 hydroxyalkyl (meth) acrylate; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and the like. Each can be used alone or in combination of two or more Kill.

  The fatty acid and the hydroxyl group-containing polymerizable unsaturated monomer usually have an equivalent ratio of carboxyl group in the fatty acid to hydroxyl group in the hydroxyl group-containing monomer of 0.4: 1 to 1.25: 1, preferably 0.5: The reaction can be carried out at such a ratio that it is within the range of 1 to 1.2: 1.

  The reaction between the fatty acid and the hydroxyl group-containing polymerizable unsaturated monomer is usually carried out in the presence of a polymerization inhibitor without causing a reaction problem such as gelation and the carboxyl group in the fatty acid component and the hydroxyl group-containing polymerizable monomer. The reaction can be carried out under conditions that allow the hydroxyl group in the saturated monomer to react smoothly, and usually by heating at a temperature of about 100 to about 180 ° C. for about 0.5 to about 10 hours in the presence of an esterification catalyst. Suitable to do. Examples of the esterification catalyst include sulfuric acid, aluminum sulfate, potassium hydrogen sulfate, alkyl-substituted benzene, hydrochloric acid, methyl sulfate, phosphoric acid, and the like. These catalysts are usually used to react with the above fatty acid to be reacted with a hydroxyl group-containing polymerizable monomer. It can be used in the range of about 0.001 to about 2.0% by weight, based on the total amount of saturated monomers. Furthermore, an organic solvent inert to the reaction can also be used.

  As the polymerization inhibitor, similar to the reaction of a fatty acid and an epoxy group-containing polymerizable unsaturated monomer, known polymerization inhibitors can be used alone or in combination of two or more.

  In the fluorine-containing aqueous resin composition (I) of the present invention, the fluorine-containing polymerizable unsaturated monomer (a), the acid group-containing polymerizable unsaturated monomer (b), the hydrophilic group-containing polymerizable unsaturated monomer (c) In addition to the polymerizable unsaturated monomer (d) having a functional group other than acid groups and hydrophilic groups, other polymerizable unsaturated monomers (e) can be copolymerized as necessary. Other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylmethylcyclohexyl (meth) acrylate, cyclodode Alkyl or cycloalkyl (meth) acrylates such as ru (meth) acrylate; Vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; Vinyl ester compounds such as vinyl acetate; Fumarate ester compounds; Butyl vinyl ether, cyclohexyl vinyl ether And vinyl ether compounds such as triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, propenyl ether propylene carbonate, vinyl ether-terminated urethane oligomer obtained by reacting hydroxybutyl vinyl ether and isocyanate, and the like. Species or two or more types can be used in combination.

  In the fluorine-containing aqueous resin composition (I) in the present invention, the total amount of the acid group-containing polymerizable unsaturated monomer (b) and the hydrophilic group-containing polymerizable unsaturated monomer (c) is the fluorine-containing aqueous resin composition. In order to express the hydrophilicity of the coating film by the aqueous paint blended with (I), it exceeds 30% by mass based on the total amount of all polymerizable unsaturated monomers in the fluorine-containing aqueous resin composition (I). It is preferable that it is a thing, More preferably, it exists in the range of 45-85 mass%.

  In the fluorine-containing aqueous resin composition (I) in the present invention, the fluorine-containing polymerizable unsaturated monomer (a), the acid group-containing polymerizable unsaturated monomer (b), the hydrophilic group-containing polymerizable unsaturated monomer (c), A preferred use ratio of the polymerizable unsaturated monomer (d) having a crosslinkable functional group and the polymerizable unsaturated monomer (e) is the total of all polymerizable unsaturated monomers in the fluorine-containing aqueous resin composition (I). Based on the amount, the fluorine-containing polymerizable unsaturated monomer (a) is 1 to 50% by mass, preferably 5 to 30% by mass, and the acid group-containing polymerizable unsaturated monomer (b) is 1 to 90% by mass, preferably 5 to 40% by mass, hydrophilic group-containing polymerizable unsaturated monomer (c) is 1 to 90% by mass, preferably 25 to 80% by mass, and polymerizable unsaturated monomer (d) having a crosslinkable functional group is 1 to 1% by mass. 50% by weight, preferably 5 to 40 mass%, other polymerizable unsaturated monomer (e) is 0 to 60 wt%, preferably 0 to 40 mass%.

  In the production of the fluorine-containing aqueous resin composition (I) in the present invention, the copolymerization of the polymerizable unsaturated monomer can be performed by a conventionally known method, such as a solution polymerization method, a bulk polymerization method, or an emulsion polymerization method. Can be manufactured. In the present invention, since it is easy to prepare the weight average molecular weight within a predetermined range, it is preferably produced by a solution polymerization method performed in the presence of a polymerization initiator.

  As the polymerization initiator, conventionally known ones used in the solution polymerization method can be used without limitation, for example, benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, t-butylperoxy 2-ethyl. And organic peroxides such as hexanoate; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.

  The amount of the polymerization initiator used is 0.001 to 15% by mass, preferably based on the total mass of all polymerizable unsaturated monomers used in the fluorine-containing aqueous resin composition (I) of the present invention. It is preferable in the range of 0.2-8 mass% from the point of adjusting to the weight average molecular weight mentioned later.

  The organic solvent that can be used when performing the solution polymerization method is preferably hydrophilic, for example, glycol ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, hexyl cellosolve, acetic acid. Ethylene glycol monomethyl ether, methyl methoxy butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl and propylene glycol monobutyl ether, ether ester solvent methoxybutyl acetate, alcohol solvent methyl alcohol, ethyl alcohol , Isopropyl alcohol, 2-ethylhexyl alcohol and n-butyl alcohol n-methylpyrrolidone and the like can be mentioned, but those which are inert with respect to the functional group in the polymerizable unsaturated monomer (d) having a crosslinkable functional group are appropriately selected, and one or two or more are mixed. Can be used.

  The fluorine-containing aqueous resin composition (I) in the present invention has a weight average molecular weight in the range of 1000 to 50000, and the fluorine-containing aqueous resin composition (I) of the present invention is mixed with the aqueous binder resin (II). In the case of caulking, it is preferable from the viewpoint of the orientation to the surface in the coating film obtained by painting, and more preferably within the range of 3000 to 30000. The weight average molecular weight means a numerical value obtained by converting the weight average molecular weight measured by HLC8120GPS (trade name, gel permeation chromatogram, manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. The column uses four TSKgel G-4000H × L, TSKgel G-3000H × L, TSKgel G-2500H × L, TSKgel G-2000H × L (all trade names, manufactured by Tosoh Corporation), and as a moving layer Used tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min. Detector: Measurement was performed under RI conditions.

  The acid value of the fluorine-containing aqueous resin composition (I) in the present invention is preferably in the range of 10 to 400 mgKOH / g, more preferably in the range of 20 to 400 mgKOH / g, from the viewpoint of ensuring water solubility. It is. Here, the acid value represents the mass of potassium hydroxide corresponding to the same molar amount as that of the acid group contained in 1 g (solid content) of the sample, in mg unit.

  Next, the aqueous binder resin (II) other than the fluorine-containing aqueous resin composition (I) in the present invention will be described.

  As the aqueous binder resin (II), a resin that can be generally applied to an aqueous coating composition other than the fluorine-containing aqueous resin composition (I) can be used without particular limitation. For example, a resin that can be dissolved or dispersed in water can be used. Specific examples include acrylic resins, polyolefin resins, silicone resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, and the like. Or in combination of two or more. Alternatively, these resins may be modified or graft polymerized.

  When the aqueous binder resin (II) is in the form of dispersed particles, the aqueous binder resin (II) may be a single layer or a multilayer such as a core / shell type. From the viewpoint of compatibility with the fluorine-containing aqueous resin composition (I) and the storage stability of the aqueous resin composition, it may be a resin having an anionic group, particularly a carboxyl group as a hydrophilic group. In this case, it may be neutralized in the aqueous resin composition. Any conventionally known neutralizing agent can be used without limitation. Examples thereof include aliphatic tertiary amines, and specifically, triethylamine, N, N-dimethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine, triethanolamine and the like can be used. . These can be used alone or in combination of two or more.

In the aqueous resin composition of the present invention, as the aqueous binder resin (II), an acrylic resin having the following polymerizable unsaturated monomer as a copolymer component is used from the viewpoint of the weather resistance of a coating film obtained by coating. It is preferable to do. Specific examples of the polymerizable unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert- Butyl (meth) acrylate, pentyl (meth) acrylate, methylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Linear or branched (meth) acrylates having linear or branched hydrocarbon groups such as lauryl (meth) acrylate and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Alicyclic (meth) acrylate; Aralkyl (meth) acrylate such as benzyl (meth) acrylate; Alkoxyethyl 2-methoxyethyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate Perfluoroalkyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide, (meth) acrylonitrile; vinyl ester compound such as vinyl acetate; vinyl such as styrene, α-methylstyrene, vinyltoluene Aromatic compounds: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, 1.4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxylmethylethanedi (meth) acrylate, 1,1,1-trishydroxylmethylpropanedi (meth) Polyvinyl compounds having two or more polymerizable unsaturated groups in one molecule such as acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc .; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; ε-caprolactone modified form of the above hydroxyalkyl (meth) acrylate; molecular terminal is a hydroxyl group Polyoxyethylene chain-containing (meth) acrylate; hydroxyl group-containing polymerizable unsaturated monomer such as allyl alcohol; carboxyl group-containing polymerizability such as (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, β-carboxyethyl acrylate Tired Sum monomers; (meth) acrolein, formylstyrene; C4-C7 vinyl alkyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone; acetoacetoxyethyl, acetoacetoxyallyl (meth) acrylate, diacetone (meth) acrylamide, etc. Carbonyl group-containing polymerizable unsaturated monomers: glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3 , 4-Epoxycyclohexylpropyl (meth) acrylate, epoxy group-containing polymerizable unsaturated monomers such as allyl glycidyl ether; isocyanate ethyl (meth) acrylate, m-isopropenyl Isocyanate group-containing polymerizable unsaturated monomers such as α, α-dimethylbenzyl isocyanate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane , Γ- (meth) acryloyloxypropyltriethoxysilane and other polymerizable unsaturated monomers having an alkoxysilyl group; epoxy group-containing polymerizable unsaturated monomers or hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids Oxidizable curable group-containing polymerizable unsaturated monomers such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like. 2 or more In combination can be used.

  The polymerization method of the polymerizable unsaturated monomer can be performed by a conventionally known method, and can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or the like. In this invention, it is preferable to manufacture by the emulsion polymerization method from the point of the physical property of the coating film obtained by apply | coating an aqueous coating composition.

  As the emulsifier used in the emulsion polymerization of the aqueous binder resin (II), an anionic emulsifier and a nonionic emulsifier are suitable. Examples of the anionic emulsifier include alkyl sulfonic acid, alkyl benzene sulfonic acid, and alkyl phosphoric acid. Examples of the nonionic emulsifier include polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, and polyoxyethylene phenyl ether. , Polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monoio Benzoate, sorbitan monolaurate, sorbitan monostearate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and the like. Also, a polyoxyalkylene group-containing anionic emulsifier having an anionic group and a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group in one molecule, or the anionic group and polymerizable unsaturated in one molecule Reactive anionic emulsifiers having groups may be used. The emulsifier can be used in the range of 0.5 to 6% by mass, preferably 1 to 4% by mass, based on the total amount of all monomers used.

  In the aqueous resin composition of the present invention, when the aqueous binder resin (II) is a carbonyl group-containing aqueous resin, the water resistance of the coating film obtained by coating can be improved by further adding a hydrazine derivative. There is an effect to improve. Specific examples of the hydrazine derivatives include saturated dicarboxylic acid dihydrazides having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. Monoolefinic unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid dihydrazide, terephthalic acid dihydrazide or isophthalic acid dihydrazide; pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydride Citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphtho Tetrahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride); hydrazide group-containing compound such as carbonic dihydrazide; bissemicarbazide; hexamethylene diisocyanate Polyfunctional semicarbazide obtained by excessively reacting N, N-substituted hydrazine such as N, N-dimethylhydrazine or the above-mentioned hydrazide with a diisocyanate such as diphenyl isocyanate or isophorone diisocyanate or a polyisocyanate compound derived therefrom, and the polyisocyanate compound Diisocyanate group in the reaction product of the active hydrogen compound containing a hydrophilic group such as polyether and polyol or polyethylene glycol monoalkyl ether. Aqueous polyfunctional semicarbazide obtained by excessively reacting the hydrazide; compounds having a semicarbazide group, such as a mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide; compound having a hydrazone group, such as bis-acetyl-di hydrazone and the like.

  The hydrazine derivative generally has a hydrazide group, a semicarbazide group and a hydrazone group contained in the hydrazine derivative in a range of 0.01 to 2 mol with respect to 1 mol of the carbonyl group in the aqueous binder resin (II). Preferably, it is in the range of 0.1 to 1.5 mol.

  In the aqueous resin composition of the present invention, the amount of the fluorine-containing aqueous resin composition (I) is more than 0 and less than 15% by mass as a solid content with respect to the aqueous binder resin (II). Is preferable in terms of achieving both hydrophilicity and water resistance of a coating film obtained by coating, and it is particularly preferably in the range of 0.2 to 8% by mass.

  The water-based coating composition of the present invention may further include a coloring pigment, a rheology control agent, a pigment dispersant, an anti-settling agent, a curing catalyst, an antifoaming agent, an antioxidant, and an ultraviolet absorber, as necessary. Various additives such as agents, extender pigments and the like can be appropriately blended and mixed and dispersed.

Next, an Example is given and this invention is demonstrated more concretely. Here, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.

Production of fatty acid-modified polymerizable unsaturated monomer Production Example 1
The following components were placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and reacted at a reaction temperature of 140 ° C. for 5 hours while stirring to obtain a fatty acid-modified polymerizable unsaturated monomer (a-1).
Safflower oil fatty acid 280 parts Glycidyl methacrylate 142 parts
Production of acrylic resin solution Production example 2
A four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was charged with 70 parts of propylene glycol monomethyl ether, heated to 110 ° C. with stirring, and the temperature of the liquid in the four-necked flask Was maintained at 110 ° C., and a mixture of the monomer, solvent and polymerization initiator shown in Table 1 below was added dropwise at a constant rate over 3 hours. After the completion of dropping, the temperature is kept at 110 ° C. for 1.5 hours, and then an initiator solution prepared by dissolving 0.5 part of an additional polymerization initiator in 10 parts of propylene glycol monomethyl ether is dropped at a constant rate over 1.5 hours. The temperature was kept at 110 ° C. for 3 hours and stirring was continued. An acrylic resin solution (F1) was obtained. The weight average molecular weight of the obtained resin was about 4,200. The non-volatile content was 43%, and the acid value was 78 mgKOH / g.
(Note 1) “Blemmer PME-400”: Product names, Japanese fats and oils, Methoxypolyoxyethylene group-containing methacrylate production examples 3 to 15 having an average number of oxyethylene groups of 9
Except having shown a compounding composition in Table 1, it carried out similarly to manufacture example 2, and obtained each acrylic resin solution (F2)-(F14). The property values of the obtained resin solution are also shown in Table 1.

Production of reactive carbonyl group-containing emulsion resin Production Example 16
3 parts of deionized water and 2.3 parts of “Newcol 707SF” (Note 2) were added to a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, and maintained at 80 ° C. after nitrogen substitution. . Immediately before the pre-emulsion having the following composition was dropped into the four-necked flask, 0.7 part of ammonium persulfate was added, and the pre-emulsion was dropped over 3 hours.
Deionized water 338 parts Diacetone acrylamide 32 parts Acrylic acid 3.2 parts Styrene 97 parts Methyl methacrylate 260 parts 2-Ethylhexyl acrylate 100 parts n-butyl acrylate 150 parts “Newcol 707SF” (Note 2) 62 parts Ammonium persulfate 1.2 parts From 30 minutes after the completion of dropping, a solution of 0.7 parts of ammonium persulfate dissolved in 7 parts of deionized water was added dropwise for 30 minutes, held at 80 ° C. for 2 hours, and then cooled to about 40-60 ° C. The pH was adjusted to 8-9 with aqueous ammonia to obtain a reactive carbonyl group-containing emulsion resin (A-1) having a solid content of 51.2%. The weight average molecular weight of this resin was 100,000 or more, and the average particle diameter was 160 nm as measured using a quasi-elastic light scattering method according to “Coulter N4 model” of Coulter.
(Note 2) “Newcol 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain, 30% active ingredient.

Production of fatty acid-modified resin emulsion Production Example 17
After preparing the preliminary emulsified liquid by putting the following components into a glass beaker and using a rotary stirrer equipped with a stirring blade that stirs the liquid in the glass beaker, holding at 2000 rpm and stirring for 15 minutes. The pre-emulsified liquid was subjected to a high-pressure treatment at 100 MPa in a high-pressure emulsifier that collides fluids by applying high-pressure energy, thereby obtaining a monomer emulsion having an average particle diameter of 190 nm of dispersed particles.

Fatty acid-modified polymerizable unsaturated monomer (a-1) 30.15 parts styrene 15 parts 2-hydroxyethyl methacrylate 4.5 parts i-butyl methacrylate 20.35 parts t-butyl methacrylate 20 parts 2-ethylhexyl acrylate 8 parts methacrylic acid 2 parts n-octyl-3-mercaptopropionate 0.3 part “Newcol 707SF” 10 parts deionized water 85 parts

Next, the monomer emulsion was transferred to a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, and diluted with deionized water to a solid content concentration of 45%. Thereafter, the temperature was raised to 85 ° C., and an initiator aqueous solution in which 2 parts of “VA-086” (Note 3) was dissolved in 10 parts of deionized water was added to the flask and stirred for 3 hours while maintaining the temperature. Thereafter, an initiator aqueous solution in which 0.5 part of “VA-086” was dissolved in 10 parts of deionized water was added to the flask, stirred for 1 hour while maintaining the temperature, cooled to 40 ° C., and dimethylaminoethanol. The pH was adjusted to 8.0 to obtain a fatty acid-containing emulsion resin (A-2) having a solid content of 40% and an average particle size of the dispersed resin of 165 nm.
(Note 3) “VA-086”: trade name, manufactured by Wako Pure Chemical Industries, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide].

Production Example 1 of water-based coating composition
195 parts of the reactive carbonyl group-containing emulsion resin (A-1) obtained in Production Example 16 is blended in a stainless steel beaker, and a rotary stirrer equipped with a stirring blade for stirring the liquid in the stainless steel beaker is used. And stirred. While stirring, 0.5 part of the acrylic resin solution (F1) obtained in Production Example 2 was added, and 3 parts of adipic acid dihydrazide and 10 parts of “Texanol” (Note 4) were added, followed by mixing and stirring. A coating composition 1 was obtained.
(Note 4) “Texanol”: trade name, manufactured by Eastman Kodak Company, 2,2,4-trimethylpentanediol monoisobutyrate.

Examples 2-12 and Comparative Examples 1-6
In Example 1, except that the blending composition was as described in Table 2, it was carried out in the same manner as in Example 1 to obtain each aqueous coating composition.
(Note 5) “DICnate 3111”: trade name, manufactured by Dainippon Ink & Chemicals, Ltd., dryer, Co content 3%).

Preparation of test plate Using a doctor blade on each of the two degreased washed glass plates obtained in Examples 1-12 and Comparative Examples 1-6, dried The coating was applied to a coating thickness of 60 μm and dried at 20 ° C. for 1 week to prepare a test plate for an evaluation test.

Evaluation test The following evaluation tests (1) to (3) were carried out using the aqueous coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 and a test plate, and the results are shown in Table 2. It was shown to.
(1) Storage stability Put 80 ml of each water-based paint composition in a 100 ml glass wide-mouthed bottle, seal it tightly, and store it in a thermostatic bath at 50 ° C. for 1 month. And evaluated.
5: No change is observed at all.
4: A slight increase in viscosity is observed, but the paint can be applied as it is.
3: The viscosity increases and a small amount of sediment is generated, but it becomes uniform by manual stirring.
2: Viscosity increases, precipitates are generated, and stirring is difficult.
1: Sedimentation is remarkable, solid-liquid separation is impossible and stirring is impossible.
(2) Water wettability: The water wettability was evaluated by the water wet area ratio when the test plate was immersed in a water tank filled with tap water for 30 seconds and pulled up.
5: Water wet area 90-100%
4: Water wet area 80 to less than 90% 3: Water wet area 70 to less than 80% 2: Water wet area 50 to less than 70% 1: Water wet area less than 50%

In addition, evaluation of water wettability is the initial stage (after coating, left at 20 ° C. for 7 days), after water immersion (after the initial evaluation, the test plate filled with tap water) for the above-mentioned Examples and Comparative Examples; The tap water was allowed to continuously flow in and overflowed, and after being immersed for 500 hours and then pulled up, it was allowed to stand in an environment of 20 ° C. and 75% RH for 24 hours.

If the water-wetting area ratio was 70% or more, it was evaluated that good contamination resistance was exhibited.
(3) Water resistance After each test plate was immersed in clean water at 20 ° C. for 7 days, the coated surface state was observed and evaluated according to the following criteria.
5: Good 4: Slightly cloudy 3: Partially blistered 2: Blistered on the entire surface 1: Partially peeled

The aqueous resin composition of the present invention can be applied to a building exterior and a steel structure as an aqueous coating composition.

Claims (4)

Fluorine-containing polymerizable unsaturated monomer (a), acid group-containing polymerizable unsaturated monomer (b), hydrophilic group-containing polymerizable unsaturated monomer selected from hydroxyl group, alkoxypolyoxyalkylene group, amide group and morpholino group ( c), a fluorine-containing aqueous resin composition obtained by copolymerizing a polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group and, if necessary, another polymerizable unsaturated monomer (e). An aqueous resin composition comprising (I) and an aqueous binder resin (II) other than (I) having a reactive group with a polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group And the functional group other than the acid group and the hydrophilic group in the polymerizable unsaturated monomer (d) having a functional group other than the acid group and the hydrophilic group of the fluorine-containing aqueous resin composition (I) is an epoxy group, Isocyan Over preparative group, the amount of isocyanate groups protected with alcohol or oxime, carbonyl group, radically polymerizable and fluorine-containing aqueous resin composition I der those selected from the group having an unsaturated bond (I) is An aqueous resin composition having a solid content of more than 0 and less than 15% by mass with respect to the aqueous binder resin (II) . A group or ketone having a carbon-carbon double bond derived from an unsaturated fatty acid in which the functional group of the polymerizable unsaturated monomer (d) having a functional group other than an acid group and a hydrophilic group is a radical polymerizable unsaturated bond The aqueous resin composition according to claim 1, wherein the aqueous resin composition is at least one group selected from the group consisting of ionic carbonyl groups. The fluorine-containing aqueous resin composition (I) is a fluorine-containing polymerizable unsaturated monomer (a) 1-50.
%, Acid group-containing polymerizable unsaturated monomer (b) 1 to 90% by weight, hydrophilic group-containing polymerizable unsaturated
1 to 90% by weight of monomer (c), polymerizable unsaturated monomer having a functional group other than acid group and hydrophilic group
Nomer (d) 1-50 mass% and other polymerizable unsaturated monomer (e) 0-60 mass%
The aqueous resin composition according to claim 1, wherein the aqueous resin composition is a copolymer of a monomer mixture . The water-based coating composition containing the water-based resin composition of any one of Claims 1-3 .