JP4637471B2 - Water-based paint composition - Google Patents

Description

  The present invention relates to an aqueous coating composition exhibiting excellent permeability, reinforcement and adhesion to a base.

In buildings and civil engineering structures, various top coats are applied for the purpose of beautifying and protecting the surface. However, there are a wide variety of base materials and existing coating films used as the foundation to be constructed, and it is necessary to apply a paint suitable for each foundation.
As such paints, various solvent-based and water-based paints are provided. Applicability to the base is judged, and an optimum one is appropriately selected from many paints and used.

  In general, solvent-based paints are widely used because they exhibit excellent permeability, reinforcement and adhesion to the base.

  However, in recent years, there has been a shift from solvent-based to water-based systems due to problems of environmental hygiene and work safety, and recently, water-based paints exhibiting the same performance as solvent-based paints are eagerly desired.

  In addition, water-based paints have excellent permeability, reinforcement, and adhesion to the base, and water-based undercoat paints that have excellent adhesion to the top coat and are superior to the base in terms of shortening the work period. There is also a growing demand for water-based topcoats that do not require primer coatings that exhibit penetrability, reinforcement, and adhesion.

Examples of water-based paints include, for example, Patent Document 1, an emulsion containing amino acid groups containing copolymer fine particles having a number average molecular weight of 1000 to 10,000 of a glycidyl group-containing monomer and an ethylenically unsaturated monomer. A water-based paint using cross-linking of epoxy groups and amino groups, which is a combination of emulsions containing copolymer fine particles having a number average molecular weight of 1000 to 10000 of a monomer and an ethylenically unsaturated monomer, is described Has been.
In Patent Document 1, by combining an emulsion containing an amino group having a low average molecular weight and an emulsion containing an epoxy group, the permeability to the substrate is improved, and the reinforcing property to the substrate by the crosslinking reaction of the amino group and the epoxy group is improved. We are trying to improve.

Japanese Patent Laid-Open No. 6-73334

However, in some amino groups penetrating into the base, there may be amino groups remaining without reacting with the epoxy group. In general, amino groups are easy to take up moisture, and if amino groups remain in the base, moisture easily enters from the back of the base, and the water entering the base has an adverse effect on the coating film, resulting in a decrease in water resistance of the coating film. In some cases, it may cause problems such as swelling and peeling.
In addition, the carboxyl group, which is widely used as a functional group that improves the storage stability of paints, has the property of easily taking in moisture containing alkali components that intrude from the back of the base, which has an adverse effect on the coating film. There was a case.

In order to solve these problems, the present inventor has intensively studied, and as a result,
In the first invention, in the particle size distribution of the synthetic resin emulsion having a specific particle size, an aqueous coating composition containing a synthetic resin emulsion containing a small amount of amino group and carboxyl group-containing monomer components in a small particle component Found to show excellent permeability, reinforcement and adhesion to
Furthermore, in the second invention, in the particle size distribution of the synthetic resin emulsion having a specific particle size, the small particle component contains a synthetic resin emulsion with a small amount of amino group and carboxyl group-containing monomer components, By including a synthetic resin emulsion containing a certain amount of amino group-containing monomer component in the large particle component, it exhibits excellent permeability, reinforcement and adhesion to the base, and also for top coating A water-based coating composition suitable for undercoating that exhibits excellent adhesion is found,
Further, in the third invention, in the particle size distribution of the synthetic resin emulsion having a specific particle size, the synthetic resin emulsion containing a small amount of amino group and carboxyl group-containing monomer components is contained in the small particle component. By including a synthetic resin emulsion with a small amount of amino group-containing monomer component in a large particle component, it exhibits excellent permeability, reinforcement and adhesion to the substrate, as well as excellent water resistance on the coating surface. That is, a water-based paint composition suitable as a top coat that does not require a base coat is found,
The present invention has been completed.

That is, the present invention has the following characteristics.
First Invention The following 1. ~ 2. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a Amino group-containing monomer and 1 the total amount of the carboxyl group-containing monomer of the second aspect of the present invention following below 0.2% by weight. ~ 3. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a The total amount is less than 0.2 wt% in weight ratio 3 of amino group-containing monomers and carboxyl group-containing monomer. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer components 1 the following inventions of the amino group-containing monomer The following 10 wt% 0.1 wt% or more by weight ratio of 3. ~ 3. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a The total amount is less than 0.2 wt% in weight ratio 3 of amino group-containing monomers and carboxyl group-containing monomer. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer components Amino group-containing monomer in a weight ratio less than 0.1 wt%

  The water-based coating composition of the first invention of the present invention exhibits excellent permeability, reinforcement and adhesion to the base. The water-based coating composition of the second invention exhibits excellent permeability, reinforcement and adhesion to the base, and is excellent in adhesion with the top coating, and is particularly suitable as a primer coating. The water-based coating composition of the third invention exhibits excellent permeability, reinforcement and adhesion to the base, and also has excellent water resistance on the surface of the coating film. Is preferred.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The aqueous coating composition of the present invention comprises a synthetic resin emulsion as a resin component, and exhibits excellent permeability, reinforcement, and adhesion to all bases as described below.

In such a synthetic resin emulsion, in the first invention,
1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all the particles have a particle size of 90 nm or less,
2. In the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles in the range from 0% to less than 5% (hereinafter also referred to as “small particle component”) from the smaller particle size side, amino groups The total amount of the containing monomer and the carboxyl group-containing monomer is less than 0.2% by weight by weight,
It is characterized by being.

In the present invention, the particle size distribution and the particle size are measured by a dynamic light scattering method.
Specifically, as a dynamic light scattering measurement device, using a Microtrac particle size analyzer (for example, UPA150, Nikkiso Co., Ltd.), the detected scattering intensity is a value analyzed by the Marquardt method of the histogram analysis method, The measurement temperature is 25 ° C.

  In the particle size distribution of the synthetic resin emulsion, particles of 5% or more and 80% or less of all particles have a particle size of 90 nm or less, thereby obtaining an aqueous coating composition having excellent penetrability and reinforcement for all bases. be able to. In the particle size distribution, the maximum value may be one or plural. When the particle size distribution is less than 5% in the range of 90 nm or less, it hardly penetrates into the base and the reinforcing effect is inferior. On the other hand, when the content is more than 80%, it is difficult to form a continuous coating film on the base surface, and the sealing property is poor.

  Furthermore, in the particle size distribution of the synthetic resin emulsion, it is preferable that 90% or more of all the particles have a particle size of 300 nm or less. By being in such a range, it is possible to obtain a water-based coating composition having more excellent penetrability and reinforcing property for all bases.

  In the synthetic resin emulsion, the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is less than 0.2% by weight (preferably among the monomer components of the polymer constituting the small particle component). Is 0.1% by weight or less, more preferably 0% by weight).

  In general, as the particle size of the synthetic resin emulsion becomes smaller, it easily penetrates into the base, deeply penetrates into the base, and exhibits a reinforcing effect. In general, amino groups and carboxyl groups are widely used as components for improving adhesion to a base and storage stability.

  However, amino groups and carboxyl groups tend to absorb moisture, and if such a functional group is present in the coating film, the water resistance of the coating film may decrease. In particular, when amino groups and carboxyl groups are present in the component that penetrates deeply into the base, moisture easily enters from the back side, water resistance of the coating film decreases, and problems such as swelling and peeling of the coating film occur. It becomes one of the causes that cause.

  In the present invention, the total amount of amino group-containing monomer and carboxyl group-containing monomer is 0.2% by weight in the monomer component of the polymer constituting the small particle component that is most easily penetrated into the base. By being less than this, it is possible to prevent water from entering from the back side of the base and to form a coating film having excellent water resistance. When the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is 0.2% by weight or more, it becomes difficult to prevent water from entering from the back side of the base, and the water resistance is improved. Lowers and adversely affects adhesion.

As the monomer component of the polymer constituting the small particle component, those containing an epoxy group-containing monomer are preferable. By containing an epoxy group-containing monomer, it is possible to obtain an aqueous coating composition having excellent adhesion to the base due to the polarity of the epoxy group.
Furthermore, when an amino group and / or carboxyl group-containing monomer is contained in the small particle component, it reacts with the amino group and the carboxyl group to enhance the reinforcing property with respect to the base, and can exhibit excellent water resistance and adhesion.

  The weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less, among the monomer components of the polymer constituting the small particle component.

Furthermore, in the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side, an amino group-containing monomer and a carboxyl group-containing monomer are included. It is preferable that the weight ratio is 0.2% by weight or more and 10% by weight or less, more preferably 0.3% by weight or more and 8% by weight or less.
By being in such a range, while being excellent in adhesiveness with the foundation | substrate, the water-based coating composition excellent also in storage stability can be obtained.

The synthetic resin emulsion of the second invention is
1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all the particles have a particle size of 90 nm or less,
2. In the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles (small particle component) in the range of 0% to less than 5% from the smaller particle size side, amino group-containing monomer and carboxyl The total amount of group-containing monomers is less than 0.2% by weight,
3. In the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side (hereinafter also referred to as “large particle component”), amino groups Containing monomer is 0.1 wt% or more and 10 wt% or less by weight,
It is characterized by being.

  That is, the synthetic resin emulsion of the second invention is the same as that of the first invention. 2. In addition, among the monomer components of the polymer constituting the large particle component, the amino group-containing monomer is 0.1% by weight to 10% by weight, preferably 0.1% by weight to 8% by weight. It is characterized by the following.

Such a large particle component is a component that mainly forms a coating film on the surface of the base, although a component that penetrates the base is included depending on the type of the base. Among the monomer components of the polymer constituting such a large particle component, the amino group-containing monomer is 0.1 wt% or more and 10 wt% or less in weight ratio, thereby improving the adhesion with the top coating material. An excellent aqueous coating composition can be obtained. Furthermore, the adhesion to the ground can be enhanced.
Therefore, the water-based coating composition of the second invention is a water-based coating composition suitable as a primer coating.

  In 2nd invention, it is preferable to contain a carboxyl group-containing monomer as a monomer component of the polymer which comprises a large particle component. By containing the carboxyl group-containing monomer, an aqueous coating composition having excellent storage stability can be obtained. Specifically, among the monomer components of the polymer constituting the large particle component, the carboxyl group-containing monomer is 0.2% by weight to 10% by weight, more preferably 0.3% by weight to 8% by weight. % Or less is preferable. When the carboxyl group-containing monomer is less than 0.2% by weight, storage stability may not be improved.

  Furthermore, in the second invention, as the monomer component of the polymer constituting the large particle component, the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is 0.2% by weight or more and 10% by weight. In the following, it is further preferable that the content is 0.3 wt% or more and 8 wt% or less. By being in such a range, it is possible to obtain an aqueous coating composition that is excellent in adhesion to the base and the top coating and also excellent in storage stability.

Furthermore, in the second invention, the polymer monomer component constituting the large particle component preferably contains an epoxy group-containing monomer. By containing an epoxy group-containing monomer, it is possible to obtain an aqueous coating composition having excellent adhesion to the base due to the polarity of the epoxy group.
Such an epoxy group can react with an amino group or a carboxyl group to enhance the reinforcement to the base, and can exhibit excellent water resistance and adhesion.

  The weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less, among the monomer components of the polymer constituting the large particle component.

The synthetic resin emulsion of the third invention is
1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all the particles have a particle size of 90 nm or less,
2. In the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles (small particle component) in the range of 0% to less than 5% from the smaller particle size side, amino group-containing monomer and carboxyl The total amount of group-containing monomers is less than 0.2% by weight,
3. In the particle size distribution of the synthetic resin emulsion, among the monomer components of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side (hereinafter also referred to as “large particle component”), amino groups The containing monomer is less than 0.1% by weight by weight.

  That is, the synthetic resin emulsion of the third invention is the same as that of the first invention. 2. In addition, among the monomer components of the polymer constituting the large particle component, the amino group-containing monomer is less than 0.1% by weight, preferably 0.08% by weight or less. .

Such a large particle component is a component that mainly forms a coating film on the surface of the base, although a component that penetrates the base is included depending on the type of the base. Among the monomer components of the polymer constituting such a large particle component, the water-based paint composition having excellent water resistance on the coating film surface when the amino group-containing monomer is less than 0.1% by weight. You can get things.
Therefore, the water-based coating composition of the third invention is a water-based coating composition suitable as a top coating that does not require a base coating.

  Furthermore, in the third invention, it is preferable to contain a carboxyl group-containing monomer as a monomer component of the polymer constituting the large particle component. By containing the carboxyl group-containing monomer, an aqueous coating composition having excellent storage stability can be obtained. Specifically, it is preferable that the carboxyl group-containing monomer is 0.2 to 10% by weight, more preferably 0.3 to 8% by weight. When the carboxyl group-containing monomer is less than 0.2% by weight, the storage stability may not be improved, and when it is more than 10% by weight, the water resistance may be poor.

  Such a synthetic resin emulsion can be polymerized and produced by a known method. Moreover, it can also be produced by blending two or more synthetic resin emulsions polymerized by a known method.

As a monomer component constituting the synthetic resin emulsion,
Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, cinnamic acid;
Primary amino group-containing monomers such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene body;
Secondary amino group-containing monomers such as N-methylaminoethyl (meth) acrylate and Nt-butylaminoethyl (meth) acrylate;
N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N -Diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, Tertiary amino group-containing monomers such as 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine;
Glycidyl (meth) acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, ε-caprolactone-modified glycidyl (meth) acrylate, β-methylglycidyl (meta ) Epoxy group-containing monomers such as acrylates;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, Primary hydroxyl group-containing monomers such as glycerol mono (meth) acrylate;
Secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;
Oxazoline group-containing monomers maleic amide such as vinyl oxazoline and 2-propenyl 2-oxazoline, (meth) acrylamide, N-monoalkyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide Amide group-containing monomers such as N, N-dialkyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide, vinylamide;
Hydrolyzable silyl group-containing monomers such as trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acrylopropyltrimethoxysilane ;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, sec- Butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, trifluoroethyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, dodecenyl (meth) acrylate, otadecyl (meta Acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate monomers such as (meth) acrylate and 4-methoxybutyl (meth) acrylate;
Aromatic vinyl monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Vinylidene halide monomers such as vinylidene fluoride;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Examples thereof include ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ether, vinyl ketone, and silicone macromer. Among these, one kind or two or more kinds may be used in combination.

  As a method for producing a synthetic resin emulsion, for example, it can be produced by emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, oxidation-reduction polymerization, etc. in an aqueous medium or a hydrophilic medium. It can also be produced by polymerization. Moreover, it can also manufacture by disperse | distributing to an aqueous medium and a hydrophilic medium after superposition | polymerization. At this time, an initiator, an emulsifier, a dispersant, a chain transfer agent, a buffering agent, and other additives or the like can be appropriately added as necessary.

  The initiator is not particularly limited, and known ones can be used. Examples thereof include persulfates such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; azobisisobutyronitrile and its hydrochloride; cumene Organic peroxides such as hydroperoxide and t-butyl hydroperoxide: These persulfates or peroxides and metal ions such as iron ions and sodium sulfoxylate, formaldehyde, pyropyrosulfite, L-ascorbic acid And redox initiators in combination with a reducing agent such as Although these usage-amounts are not specifically limited, What is necessary is just to be about 0.1-5 weight part with respect to 100 weight part of monomer mixtures.

The emulsifier is not particularly limited and known ones can be used, such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dioctylsulfosuccinate, poly Anionic emulsifiers such as sodium oxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate;
Nonionic emulsifiers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene oxypropylene block copolymer; lauryl trimethyl ammonium chlorite, stearyl trimethyl ammonium chlorite And cationic emulsifiers such as trimethyloctadecyl ammonium chlorite. In addition, the use of a reactive emulsifier having an ethylenically unsaturated double bond is preferable because the water resistance of the film can be improved. The amount of the emulsifier used is not particularly limited, but may be about 0.01 to 20 parts by weight with respect to 100 parts by weight of the monomer mixture.

  In the present invention, by appropriately setting various conditions at the time of polymerization such as various monomers, initiators, emulsifiers, polymerization temperature, medium, etc., a synthetic resin emulsion having a target particle size at a target monomer ratio Can be manufactured.

  In the present invention, it is particularly preferable to obtain a synthetic resin emulsion by blending two or more synthetic resin emulsions produced by the above-described method.

  As a preferred form of the synthetic resin emulsion of the first invention, (a) the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is less than 0.2% by weight (preferably 0.1% by weight). %, More preferably 0% by weight) of a synthetic resin emulsion (hereinafter also referred to as “component (a)”), and component (a) mainly constitutes a small particle component.

Furthermore, what contains an epoxy group containing monomer as a monomer component of the polymer which comprises (a) component is preferable. By containing an epoxy group-containing monomer, it is possible to obtain an aqueous coating composition having excellent adhesion to the base due to the polarity of the epoxy group.
Furthermore, when an amino group and / or a carboxyl group-containing monomer is contained in the component (a) or the component (b) described later, the amino group and the carboxyl group react with each other to increase the reinforcement to the base, and have excellent water resistance, Adhesion can be shown.

  Among the monomer components of the polymer constituting the component (a), the weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less.

  Furthermore, in the first invention, a synthetic resin in which the total amount of the component (a) and the component (b) amino group-containing monomer and carboxyl group-containing monomer is 0.2% by weight or more and 20% by weight or less. It is preferable to blend an emulsion (hereinafter also referred to as “component (b)”).

  The component (b) mainly constitutes a large particle component among the particles forming the synthetic resin emulsion.

As the monomer component of the polymer constituting the component (b), the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is 0.2% by weight or more and 20% by weight or less by weight ratio, Furthermore, it is preferable that it is 0.2 to 10 weight%.
By being in such a range, it is possible to obtain an aqueous coating composition that is excellent in adhesion to the base.

As a preferable form of the synthetic resin emulsion of the second invention, the synthetic resin emulsion (hereinafter referred to as “a” component and (c) the amino group-containing monomer is 0.2% by weight or more and 20% by weight or less) And a blend of “(c) component”).
In the second invention, when the component (a) and the component (c) are blended, in the particle size distribution of all particles, the polymer constituting particles in the range of 0% or more and less than 5% from the smaller particle size side. Among the monomer components, the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is less than 0.2% by weight, and particles having a particle diameter in the range of 5% to 100% from the smaller particle diameter side. Among the monomer components of the polymer that constitutes, the amino group-containing monomer may be set to have a weight ratio of 0.1 wt% to 10 wt%.

  The component (a) mainly constitutes a small particle component among the particles forming the synthetic resin emulsion.

In 2nd invention, what contains an epoxy-group-containing monomer is preferable as a monomer component of the polymer which comprises (a) component. By containing an epoxy group-containing monomer, it is possible to obtain an aqueous coating composition having excellent adhesion to the ground due to the polarity of the epoxy group.
In addition, when the amino group and / or carboxyl group-containing monomer is included in the component (a) or component (c), it reacts with the amino group or carboxyl group to enhance the reinforcement to the substrate, and has excellent water resistance and adhesion. Can be shown.

  Among the monomer components of the polymer constituting the component (a), the weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less.

  The component (c) mainly constitutes a large particle component among the particles forming the synthetic resin emulsion.

As the monomer component of the polymer constituting the component (c), the amino group-containing monomer is 0.1 to 20% by weight, more preferably 0.1 to 10% by weight. % Or less is preferable.
By being in such a range, it is possible to obtain an aqueous coating composition that is excellent in adhesion to the base. Furthermore, the adhesiveness with the top coat can be enhanced.

  Furthermore, the component (c) preferably contains a carboxyl group-containing monomer. By containing the carboxyl group-containing monomer, an aqueous coating composition having excellent storage stability can be obtained. Specifically, in the monomer component of the polymer constituting the component (c), the carboxyl group-containing monomer is 0.2% by weight to 10% by weight, more preferably 0.3% by weight to 8% by weight. % Or less is preferable. When the carboxyl group-containing monomer is less than 0.2% by weight, the storage stability may be inferior.

  The component (c) in the second invention preferably includes both an amino group-containing monomer and a carboxyl group-containing monomer, and by including both, it is excellent in adhesion to the groundwork or top coating and storage stability. An aqueous coating composition can be obtained. Specifically, the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is 0.2% by weight to 20% by weight, more preferably 0.2% by weight to 10% by weight, in terms of weight ratio. It is preferable.

  Further, the component (c) preferably contains an epoxy group-containing monomer. By containing an epoxy group-containing monomer, when the amino group and / or carboxyl group-containing monomer is contained in the component (a) or the component (c), it reacts with the amino group and carboxyl group to reinforce the foundation. And can exhibit excellent water resistance and adhesion.

  Among the monomer components of the polymer constituting the component (c), the weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less.

The component (c) is, in particular, from a core part obtained by polymerizing at least the monomer component of the epoxy group-containing monomer, and from a shell part obtained by polymerizing at least the monomer component of the carboxyl group-containing monomer. Thus, a core-shell type synthetic resin emulsion containing at least an amino group-containing monomer as the monomer component of the polymer constituting the core part and / or the shell part is preferable. If the component (c) is such a core-shell type synthetic resin emulsion, an aqueous coating composition having better storage stability and better adhesion can be obtained.
Furthermore, the amino group-containing monomer is preferably the above-described tertiary amino group-containing monomer.

A preferred form of the synthetic resin emulsion of the third invention is a synthetic resin emulsion (hereinafter referred to as “(d)”) in which the component (a) and the component (d) amino group-containing monomer are less than 0.4% by weight. What is necessary is just to blend an "component".
In the third invention, when the component (a) and the component (d) are blended, in the particle size distribution of all particles, the polymer constituting the particles in the range of 0% or more and less than 5% from the smaller particle size side. Among the monomer components, the total amount of the amino group-containing monomer and the carboxyl group-containing monomer is less than 0.2% by weight, and particles having a particle diameter in the range of 5% to 100% from the smaller particle diameter side. The amino group-containing monomer may be set so as to be less than 0.2% by weight in the monomer component of the polymer that constitutes A.

  The component (a) mainly constitutes a small particle component among the particles forming the synthetic resin emulsion.

In 3rd invention, what contains an epoxy-group containing monomer as a monomer component of the polymer which comprises (a) component is preferable. By containing an epoxy group-containing monomer, it is possible to obtain an aqueous coating composition having excellent adhesion to the base due to the polarity of the epoxy group.
In addition, when the amino group and / or carboxyl group-containing monomer is included in the component (a) or component (d), it reacts with the amino group or carboxyl group to enhance the reinforcement to the substrate, and has excellent water resistance and adhesion. Can be shown.

  Among the monomer components of the polymer constituting the component (a), the weight ratio of the epoxy group-containing monomer is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less.

  The component (d) mainly constitutes a large particle component among the particles forming the synthetic resin emulsion.

As the monomer component of the polymer constituting the component (d), the amino group-containing monomer is less than 0.4% by weight, more preferably less than 0.2% by weight, and further 0% by weight. It is preferable that
By being in such a range, the water-based coating composition which is excellent in the water resistance of the coating-film surface can be obtained.
The amino group-containing monomer is preferably the above-described tertiary amino group-containing monomer.

  Furthermore, it is preferable that (d) component contains a carboxyl group-containing monomer. By containing the carboxyl group-containing monomer, an aqueous coating composition having excellent storage stability can be obtained. Specifically, it is preferable that the carboxyl group-containing monomer is 0.2 to 10% by weight, more preferably 0.3 to 8% by weight. When the carboxyl group-containing monomer is less than 0.2% by weight, the storage stability may be inferior, and when it is more than 10% by weight, the water resistance may be inferior.

  Furthermore, the component (d) preferably has a monomer containing a reactive functional group. The reactive functional group can improve the strength of the coating film surface by a crosslinking reaction with the functional group that reacts with the reactive functional group, thereby obtaining a coating film having excellent water resistance.

  Such combinations of reactive functional groups include epoxy groups and amino groups, epoxy groups and carboxyl groups, carboxyl groups and carbodiimide groups, carboxyl groups and oxazoline groups, carbonyl groups and hydrazide groups, carboxyl groups and aziridines, Examples include decomposable silyl groups. In particular, a combination of an epoxy group and an amino group, an epoxy group and a carboxyl group, a carbonyl group and a hydrazide group, and a hydrolyzable silyl group is preferable. By having such a functional group, the coating surface has excellent water resistance. A coating film can be formed.

  Such a combination of reactive functional groups may be one having two or more reactive functional groups in the component (d), or having one or more reactive functional groups in the component (d), It may be obtained by mixing another synthetic resin emulsion or compound having a functional group that reacts with the reactive functional group.

In the present invention, a combination of hydrolyzable silyl groups is particularly preferable. By containing the monomer having such a functional group, a coating film that is more excellent in water resistance on the coating film surface can be formed.
Of the monomer components of the polymer constituting the component (d), the weight ratio of the total amount of monomers containing hydrolyzable silyl groups is preferably 0.5% by weight or more, more preferably 1.0%. % By weight or more and 20% by weight or less.

The glass transition temperature of the synthetic resin emulsion is usually −40 to 70 ° C., preferably −30 to 60 ° C., and more preferably about −20 to 50 ° C. Also when blending two or more kinds of synthetic resin emulsions, the glass transition temperature of each synthetic resin emulsion is preferably within the above range.
In particular, in the second invention, the glass transition temperature of the component (a) is preferably -40 to 50 ° C, more preferably -30 to 40 ° C, more preferably -20 to 35 ° C, and the glass of the component (c). The transition temperature is preferably −40 to 50 ° C., more preferably −30 to 40 ° C., and more preferably −20 to 35 ° C.
In the third invention, the glass transition temperature of the component (a) is preferably −40 to 50 ° C., more preferably −30 to 40 ° C., more preferably −20 to 35 ° C., and the glass of the component (d). The transition temperature is preferably -40 to 70 ° C, more preferably -30 to 60 ° C, more preferably -20 to 50 ° C.

The glass transition temperature is a value calculated from the Fox (FOX) equation. For example, in a two-component system composed of monomer (1) and monomer (2), when the glass transition points Tg (1) and Tg (2) of the respective homopolymers are known, the monomers (1) and ( The glass transition point Tg of the two-component copolymer 2) can be obtained as a calculated value from the Fox (FOX) formula (two components) shown in the following formula.
1 / Tg = W (1) / Tg (1) + W (2) / Tg (2) (W (1) + W (2) = 1)
W (1): weight fraction of monomer (1), W (2): weight fraction of monomer (2), Tg (1): Tg value of homopolymer of monomer (1) (unit: K), Tg (2): Tg value (unit: K) of homopolymer of monomer (2)
The Tg value of the polymer in the present invention is calculated by a generalized formula of the above formula to a multicomponent system.

  In the aqueous coating composition of the present invention, as a component other than the resin component, known pigments, plasticizers, film-forming aids, antiseptics, and antifungal agents that are usually used as necessary within a range not impairing the effects of the invention Antifoaming agents, viscosity modifiers, dispersants, leveling agents, flame retardants, matting agents, anti-settling agents, anti-sagging agents, ultraviolet absorbers, infrared absorbers, etc. can be used alone or in combination. . Furthermore, viscosity etc. can also be adjusted by adding water and a solvent suitably.

  Examples of pigments include, but are not limited to, heavy calcium carbonate, light calcium carbonate, clay, kaolin, talc, barium carbonate, white carbon, diatomaceous earth, cryogenic stone, porcelain clay, china clay, barite powder, barium sulfate, sedimentation Barium sulfate, silica sand, silica powder, quartz powder, resin beads, glass beads, body pigments such as hollow balloons, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt Black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine blue, bitumen, Co Inorganic colored pigments such as ruto green and cobalt blue, organic compounds such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone Examples thereof include luminescent pigments, fluorescent pigments, phosphorescent pigments, and the like, such as glass pigments, pearl pigments, aluminum pigments, glass flakes or resin films coated with metals or metal oxides, hologram pigments, and cholesteric crystal polymer pigments.

  Solvents include alcohols such as methanol, ethanol, propanol, isopropyl alcohol, and benzyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylol ethane, and glycerin, cellosolve, butyl cellosolve, and isobutyl cellosolve. , Ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, etc. can be used. . Of these solvents, it is preferable to use a hydrophilic solvent having a solubility in water of 20% by weight or more because the permeability to the base can be increased.

  The water-based paint composition of the present invention includes, for example, mortar, concrete, gypsum board, siding board, extrusion board, slate board, asbestos cement board, fiber-mixed cement board, calcium silicate board, ALC board, metal, wood, glass It can be applied to bases such as ceramics, fired tiles, porcelain tiles, plastic plates and synthetic resins, or various bases such as various existing coatings formed on such bases. Further, the present invention can be applied to a base including a sealing joint.

  In the present invention, in particular, mortar, concrete, gypsum board, siding board, extrusion board, slate board, asbestos cement board, fiber-mixed cement board, calcium silicate board, ALC board, wood, etc., or such It can be suitably applied to a base such as an existing coating film formed on the ground. When such a base is used, the effect of the present invention due to the particle size distribution of the synthetic resin emulsion can be sufficiently exhibited, which is preferable.

  The existing coating film is not particularly limited as long as it is generally used for building coating. For example, JIS K 5654 “acrylic resin enamel”, JIS K 5656 “polyurethane resin coating for building” ”, JIS K 5658“ Fluorine resin paint for construction ”, JIS K 5660“ Synthetic resin emulsion paint with gloss ”, JIS K 5663“ Synthetic resin emulsion paint ”, JIS K 5667“ Various pattern paint ”, JIS K 5668“ Synthetic resin ” Those formed of materials specified in “emulsion pattern paint”, JIS A 6909 “finishing coating material for building”, JIS A 6021 “waterproofing material for architectural coating”, and the like can be suitably used.

  The coating method of the water-based coating composition is not particularly limited and can be applied by a known method. For example, coating using various coating tools such as scissors, spatulas, brushes, sprays, rollers, and roll coaters, It can be applied by various methods such as flow coater, electrostatic coating and electrodeposition coating.

The application amount of the aqueous coating composition is not particularly limited, but is usually about 50 to 2000 g / m ² , preferably about 100 to 1500 g / m ² .
The number of times of painting is usually one time, but if necessary, the in-process interval may be set to about 0.5 hours to 7 days and may be applied a plurality of times.

The aqueous coating composition of the second invention can be suitably used as a primer coating, In this case, as the coat-weight, 50 to 2000 g / ^{m 2,} more preferably about 100 to 1000 g / ^{m 2} . Moreover, it is preferable that it is a coating amount of about 5-200 g / m < ² > as solid content of a synthetic resin emulsion.
In the second invention, the water-based paint composition can be applied and dried, and then the top-coat paint can be applied. Alternatively, the water-based paint composition can be applied and the top-coat paint can be applied undried and simultaneously dried. it can. The drying may be usually performed at room temperature, but can be performed at a high temperature as necessary. In the case of drying at room temperature, the coating interval time with the top coating is normally 0.5 hours to 7 days in the standard state (temperature 23 ° C., relative humidity 50% atmosphere), but may be longer than this. .

  Furthermore, the film formed by the aqueous coating composition of the second invention has excellent adhesion to a wide variety of top coating compositions. The top coating is not particularly limited as long as it is generally used for building coating. For example, JIS K 5654 “acrylic resin enamel”, JIS K 5656 “polyurethane resin coating for building” , JIS K 5658 “Fluorine resin paint for construction”, JIS K 5660 “Synthetic resin emulsion paint with gloss”, JIS K 5663 “Synthetic resin emulsion paint”, JIS K 5667 “Various pattern paint”, JIS K 5668 “Synthetic resin emulsion” Those specified in “pattern paint”, JIS A 6909 “finishing coating material for building”, JIS A 6021 “waterproofing material for architectural coating” and the like can be suitably used. In particular, it exhibits excellent adhesion to an elastic top coating.

  The coating method of the top coating is not particularly limited, and can be applied by a known method. For example, coating using various coating tools such as scissors, spatula, brush, spray, roller, roll coater, flow coater It can be applied by various methods such as electrostatic coating and electrodeposition coating. That is, each top coat may be applied based on the normal process with the optimum coating specifications for each top coat.

The aqueous coating composition of the third invention can be suitably used as a top coating, In this case, as the coat-weight, 100 to 2000 g / ^{m 2,} more preferably about 200~1500g / ^{m 2} .
Since the water-based coating composition of the third invention is excellent in water resistance of the coating film surface, it is not necessary to newly apply a top coating. Furthermore, since it is excellent in adhesion with the base, it is not necessary to apply a primer coating such as a sealer or a primer in advance, and the aqueous coating composition of the present invention can be directly applied to the base. Therefore, it can be finished in one process, and can greatly contribute to shortening the construction period and cost.
Further, after applying the aqueous coating composition, a top coat or the like may be applied as necessary.

  Test examples are shown below to clarify the features of the present invention.

(Test Example 1)
20 parts by weight of a synthetic resin emulsion (solid content, 40% by weight) produced at the monomer composition ratio shown in Synthesis Example 1 in Table 1, and a core-shell synthetic resin emulsion (solid content) produced at the monomer composition ratio shown in Synthesis Example 5 40 wt%), 20 parts by weight, 5 parts by weight of additives (film-forming aid, antifoaming agent, viscosity modifier) and 55 parts by weight of water were mixed at the blending ratio shown in Table 2 to produce an aqueous paint. Various tests were performed using the produced water-based paint.

  The particle size distribution of the synthetic resin emulsion was measured at a measurement temperature of 25 ° C. using a Microtrac particle size analyzer (UPA150, manufactured by Nikkiso Co., Ltd.), and the detected scattering intensity was histogramd using the attached software. The analysis was performed by the Marquardt method. The measurement results are shown in Table 1.

(Test method)
1. Storage Stability Test 250 ml of the prepared water-based paint was put into a 300 ml cup and stored in a thermostatic bath at 50 ° C. for 14 days, and the viscosity change was confirmed. The evaluation is as follows. The results are shown in Table 2.
A: Less than 20% B: Viscosity change 20% to less than 50% Δ: Viscosity change 50% to less than 80% X: Viscosity change 80% or more

2. Adhesion test On each of the substrates 1, 2, and 3 shown below, a water-based paint after storage for 14 days in a thermostatic bath at 50 ° C. was brushed at a coating amount of 150 g / m ² , temperature 23 ° C., relative humidity After drying and curing for 2 hours in a 50% atmosphere (hereinafter referred to as the standard state), a top coating (monomer composition: methyl methacrylate, styrene, 2-ethylhexyl acrylate, acrylic acid, acrylamide synthetic resin emulsion (solid content: 50%, A glossy synthetic resin emulsion paint (Tg: 20 ° C.) as a main component was sprayed at a coating amount of 300 g / m ² and dried and cured in a standard state for 7 days to obtain a test specimen. The prepared specimen was immersed in 23 ± 2 ° C. water for 18 hours in accordance with JIS K 5600-7-4, then immediately cooled in a thermostatic bath maintained at −20 ± 2 ° C. for 3 hours, and then 50 ± 2 The mixture was heated for 3 hours in a separate thermostat kept at ° C. After repeating this operation 10 times, a test specimen placed in a standard state for about 24 hours was evaluated for adhesion by a cross-cut tape method according to JIS K 5600-5-6. The evaluation is as follows. The results are shown in Table 2.
◎: The area of the peeled defect portion is less than 5%. ○: The area of the peeled defect portion is 5% or more and less than 15%. Δ: The area of the peeled defect portion is 15% or more and less than 35%. The area of the defect is 35% or more

In addition, the following was used as a base.
Base 1: 300 × 150 × 6 mm slate plate Base 2: 300 × 150 × 6 mm calcium silicate plate Base 3: 300 × 150 × 6 mm slate plate surface, Miracle Sealer ES (manufactured by SK Kaken Co., Ltd.) After spraying with a coating amount of 150 g / m ² and drying for 2 hours, SK acrylic color (manufactured by SK Kaken Co., Ltd., acrylic resin enamel) was sprayed with a coating amount of 300 g / m ² and then for one year. Outdoor exposure

(Test Examples 2 to 7)
A water-based paint was prepared in the same manner as in Test Example 1 except for the monomer composition shown in Table 1 and the paint composition shown in Table 2. A storage stability test and an adhesion test were performed using the prepared water-based paint. The results are shown in Table 2.

  In addition, all the solid content of the synthetic resin emulsion manufactured with the monomer composition ratio shown to the synthesis example 1-the synthesis example 9 is 40 weight%.

(Test Example 8)
35 parts by weight of a synthetic resin emulsion (solid content, 40% by weight) produced at the monomer composition ratio shown in Synthesis Example 1 in Table 1, and a synthetic resin emulsion (solid content, 40%) produced at the monomer composition ratio shown in Synthesis Example 6 35% by weight), 10 parts by weight of additives (film-forming aids, antifoaming agents, viscosity modifiers) and 20 parts by weight of titanium oxide were mixed at a blending ratio shown in Table 3 to produce an aqueous paint.
A storage stability test, an adhesion test, and the following water resistance test were performed using the prepared water-based paint. The results are shown in Table 3.

3. Water resistance test The base 1 was spray-coated with a water-based paint after storage for 14 days in a thermostatic bath at 50 ° C. so that the coating amount was 300 g / m ² to prepare a test specimen. The prepared specimen was dried and cured in a standard state for 7 days, and the gloss retention after immersing in 20 ° C. water for 168 hours was calculated according to JIS K 5600-1999 4.7. The evaluation is as follows.
◎: Gloss retention 90% or more ○: Gloss retention 80% or more and less than 90% △: Gloss retention 70% or more and less than 80% ×: Gloss retention 90% or less

(Test Examples 9 to 12)
A water-based paint was prepared in the same manner as in Test Example 8 except for the monomer composition in Table 1 and the paint composition in Table 3. A storage stability test, an adhesion test, and a water resistance test were performed using the prepared water-based paint. The results are shown in Table 3.

Claims (3)

The following 1. ~ 2. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a The total amount of amino group-containing monomers and carboxyl group-containing monomer in a weight ratio less than 0.2 wt% The following 1. ~ 3. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a The total amount is less than 0.2 wt% in weight ratio 3 of amino group-containing monomers and carboxyl group-containing monomer. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer components Amino group-containing monomer is more than 0.1 wt% in weight ratio 10 wt% or less The following 1. ~ 3. A water-based coating composition containing a synthetic resin emulsion that satisfies the following conditions.
1. 1. In the particle size distribution of the synthetic resin emulsion, 5% or more and 80% or less of all particles have a particle size of 90 nm or less. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 0% to less than 5% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer component, a The total amount is less than 0.2 wt% in weight ratio 3 of amino group-containing monomers and carboxyl group-containing monomer. In the particle size distribution of the synthetic resin emulsion, the monomer component of the polymer constituting the particles in the range of 5% to 100% from the smaller particle size side is a carboxyl group-containing monomer, a primary amino group-containing single amount Body, secondary amino group-containing monomer, tertiary amino group-containing monomer, epoxy group-containing monomer, primary hydroxyl group-containing monomer, secondary hydroxyl group-containing monomer, methylol group-containing monomer, Oxazoline group-containing monomer, amide group-containing monomer, hydrolyzable silyl group-containing monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinylidene halide monomer , nitrile group-containing monomer, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ethers, vinyl ketones, consist of one or more selected from a silicone macromer of the monomer components Amino group-containing monomer in a weight ratio less than 0.1 wt%