JP5828655B2 - Resin composition for paint - Google Patents

Description

The present invention relates to a coating resin composition. More specifically, the present invention relates to a coating resin composition used for forming a coating film exhibiting various functions on a substrate.

A resin composition for paint is a composition used for forming a coating film on a substrate to protect it or to improve its appearance, and is used for automobiles, railway vehicles, ships, aircraft, electrical equipment, building structures. Widely used in various fields such as goods and construction equipment. In recent years, in addition to protecting the substrate and improving the appearance, compositions that have been devised in various ways to impart various functions according to the application to the coating film have been widely used industrially, for example, various structures Resin compositions that form a coating film that exhibits vibration damping properties to prevent vibration and noise in the body and maintain quietness are used under the interior floors of automobiles, as well as railway vehicles, ships, aircraft, Widely used in electrical equipment, building structures, construction equipment, etc.
In such an industrially used coating composition, in addition to being able to form an excellent coating film, it is also an important requirement that the coating composition has high handleability, workability, and storability. Thus, the coating composition is also required to exhibit excellent mechanical stability.

As a conventional coating composition, for the purpose of providing an aqueous emulsion excellent in mechanical stability, pigment miscibility, and the like and a coating using the same, a (meth) acrylate monomer unit, a styrene monomer A polymer having at least one monomer unit selected from the group consisting of a monomer unit and a diene monomer unit is used as a dispersoid, and a vinyl alcohol polymer (A) having a specific structure and a surfactant (B ) Is included as a dispersant in a specific ratio (for example, see Patent Document 1). In addition, for the purpose of providing a copolymer latex and the like excellent in high-speed fluidity and mechanical stability of a high-concentration paint, an aliphatic conjugated diene monomer, a water-soluble ethylene monomer, and Copolymer latex containing a specific proportion of other vinyl monomers copolymerizable with these, specifying the molar ratio of potassium ion and sodium ion contained in the latex, and the zeta potential of the latex particle surface A copolymer latex is disclosed (see, for example, Patent Document 2). Furthermore, for the purpose of obtaining a latex with improved mechanical stability, a latex is produced by subjecting a specific ethylenically unsaturated monomer to aqueous emulsion polymerization in the presence of a water-soluble protective colloid such as carboxymethylcellulose. Is disclosed (for example, see Patent Document 3).

International Publication No. 2006/095524 Japanese Patent Laid-Open No. 10-204218 Japanese National Patent Publication No. 10-508632

As described above, various attempts have been made to obtain a resin composition having high mechanical stability for a resin composition used for coating. However, it is difficult to say that any of the above has achieved sufficient mechanical stability. The mechanical stability of the resin composition for paints affects not only the handling, workability and storage properties of the resin composition, but also the quality of the resulting coating film. Mechanical stability is an important factor in the composition, and there is a demand for a resin composition for coatings that has higher mechanical stability and can be more suitably used in various industrial applications.

The present invention has been made in view of the above-mentioned present situation, has high mechanical stability, excellent handleability and storage properties, and excellent workability during coating, and forms a high-quality coating film. It aims at providing the resin composition for coating materials which can be made.

As a result of various investigations on resin compositions excellent in mechanical stability that can be used for coating applications, the present inventors have found 1 to 3 masses per 100 mass% of all monomer components including monomers having acid groups. And a composition obtained by adding a sulfonate surfactant to an emulsion having a dynamic surface tension of 60 mN / m or more at 25 ° C., 10 Hz, and a solid content of 20 mass%, Then, the aggregation of emulsion particles was sufficiently suppressed, and it was found that the resin composition had excellent mechanical stability, and it was conceived that the above problem could be solved brilliantly, and reached the present invention. is there. The present invention exhibits an extremely excellent effect by the two synergistic actions of improving the stability of the particle itself by the surface design of the emulsion particle and improving the stability of the composition by selecting an additive to be added to the emulsion later. To do.

That is, the present invention is a resin composition for coatings containing an emulsion obtained by emulsion polymerization of monomer components, and the emulsion is added to 100% by mass of all monomer components including monomers having acid groups. It is obtained by using 1 to 3% by mass of an emulsifier, and has a dynamic surface tension of 60 mN / m or more at 25 ° C., 10 Hz, and a solid content of 20% by mass. It is the resin composition for coatings containing a sulfonate type surfactant with an emulsion.
The present invention is described in detail below.

The resin composition for coatings of the present invention is obtained by using 1 to 3% by weight of an emulsifier with respect to 100% by weight of all monomer components including a monomer having an acid group. An emulsion having a dynamic surface tension of 60 mN / m or more under the condition of 20% by mass (hereinafter also referred to as an emulsion in the present invention) and a sulfonate surfactant are included. Each of these emulsions and sulfonate type surfactants may contain one kind or two or more kinds.
Moreover, as long as the emulsion in this invention and the sulfonate type surfactant are included, components other than these, such as an emulsion which does not correspond to the emulsion in this invention, may be included.

The emulsion in the present invention is formed by a polymer obtained from a monomer component containing a monomer having an acid group, and the monomer component is 100% by mass of the total monomer components. On the other hand, it is preferable to contain 0.1-5 mass% of monomers having acid groups and 95-99.9 mass% of other copolymerizable monomers. By including a monomer having an acid group, aggregation of the emulsion particles is suppressed by ionic repulsion of each acid group, and a stabilization effect of the emulsion particles can be obtained. When the content of is less than 0.1% by mass with respect to 100% by mass of all monomer components, there is a possibility that such a stabilization effect of the emulsion particles cannot be sufficiently obtained. In consideration of sufficiently exhibiting properties other than mechanical stability of the resin composition containing an emulsion such as water resistance, the content of the monomer having an acid group is 100% by mass of all monomer components. On the other hand, 5 mass% or less is preferable. When the content of the monomer having an acid group exceeds 5% by mass with respect to 100% by mass of all monomer components, the water resistance of the resin coating film may be remarkably lowered. More preferably, the monomer having an acid group is 0.5 to 4% by mass, the other copolymerizable monomer is 96 to 99.5% by mass, and more preferably a monomer having an acid group. The body is 1-3% by mass, and the other copolymerizable monomer is 97-99% by mass.
In addition, when the emulsion in the present invention has a form having a core part and a shell part to be described later, a monomer component that is a raw material for the polymer that forms the core part and a raw material for the polymer that forms the shell part; The ratio of the monomer having an acid group and the other copolymerizable monomer may be as described above with respect to the total of the monomer components.

The monomer having an acid group is preferably an unsaturated carboxylic acid monomer. The unsaturated carboxylic acid monomer is not particularly limited as long as it is a compound having an unsaturated bond and a carboxyl group in the molecule, but preferably contains an ethylenically unsaturated carboxylic acid monomer.
The ethylenically unsaturated carboxylic acid monomer is not particularly limited. For example, (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, monomethyl mayate, mono 1 type, or 2 or more types, such as unsaturated carboxylic acids, such as ethyl mayate, or its derivative (s) are mentioned.
Among these, (meth) acrylic monomers are preferable.
That is, the emulsion in the present invention is an acrylic emulsion formed from an acrylic polymer obtained from a monomer component containing a (meth) acrylic monomer, which is a preferred embodiment of the present invention. One.

The (meth) acrylic acid monomer means (meth) acrylic acid and its salt. That is, in the acrylic polymer, at least one of the monomer components is C (R ¹ ₂ ) = CH—COOR ² or C (R ³ ₂ ) = C (CH ₃ ) —COOR ⁴ (R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group. It is preferable that

As the other copolymerizable monomer other than the monomer having an acid group contained in the monomer component forming the emulsion in the present invention, a copolymerizable ethylenically unsaturated monomer is preferable, which will be described later. Copolymerized with (meth) acrylic monomers other than (meth) acrylic monomers, unsaturated monomers having nitrogen atoms, unsaturated compounds having aromatic rings, and (meth) acrylic monomers Other possible monomers are included.

As the (meth) acrylic acid monomer, for example, one or more of acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and the like are used. Is preferred.
Examples of (meth) acrylic monomers other than (meth) acrylic acid monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, Butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl Methacrylate, a Octyl acrylate, isooctyl methacrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl Acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, vinyl formate, vinyl acetate, vinyl propionate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diallyl phthalate, Thoria Rucyanurate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol In addition to diacrylate, diethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, and the like, it is preferable to use one or more of these salts and esterified products.

The salt is preferably a metal salt, ammonium salt, organic amine salt or the like. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as alkaline earth metal atoms such as calcium and magnesium; aluminum, Trivalent metal atoms such as iron are suitable, and the organic amine salt is preferably an alkanolamine salt such as an ethanolamine salt, diethanolamine salt, or triethanolamine salt, or a triethylamine salt.

It is preferable that 20-80 mass% is a (meth) acrylic-acid type monomer among 100 mass% of the monomer which has the acid group which the monomer component used as the raw material of the emulsion in this invention contains. More preferably, it is 30-70 mass%.
Moreover, the monomer component used as the raw material of the emulsion in this invention is 20 masses of (meth) acrylic monomers other than (meth) acrylic acid monomers with respect to 100 mass% of all monomer components. % Or more is preferable. More preferably, it is 30 mass% or more.

As monomers other than those mentioned above, the monomer component that is the raw material of the emulsion in the present invention has an aromatic ring such as divinylbenzene, styrene, α-methylstyrene, vinyltoluene, and ethylvinylbenzene. And unsaturated compounds. Especially, it is preferable that the unsaturated compound which has an aromatic ring is included, and it is more preferable that styrene is included.
That is, the emulsion in the present invention is an acrylic styrene emulsion formed by an acrylic styrene polymer obtained from a monomer component containing styrene in addition to the (meth) acrylic monomer. It is one of the preferred embodiments of the invention.

When the emulsion in this invention is an acrylic styrene emulsion, it is preferable that the monomer component used as a raw material contains 1-50 mass% of styrene monomers with respect to 100 mass% of monomer components. More preferably, it is 5 to 45% by mass, and still more preferably 10 to 40% by mass.

As monomers other than those mentioned above, the monomer component that is the raw material of the emulsion in the present invention includes acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol. Unsaturation having nitrogen atoms such as methacrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, Ni-butoxymethyl (meth) acrylamide Compounds and the like. Among these, unsaturated compounds having a nitrogen atom are preferable. Particularly preferred is acrylonitrile.

The emulsion in the present invention is obtained by using 1 to 3% by mass of an emulsifier with respect to 100% by mass of all monomer components including the monomer having an acid group, and is 25 ° C., 10 Hz, solid content of 20% by mass. The dynamic surface tension under the conditions is 60 mN / m or more. When the dynamic surface tension under the conditions of 25 ° C., 10 Hz, and solid content of 20% by mass is 60 mN / m or more, the resin composition is used for coating applications, and the composition when applied is fluidized and stirred. Even in the state, it can be said that the emulsion has sufficient dispersibility and excellent mechanical stability. The dynamic surface tension is preferably 61 mN / m or more. More preferably, it is 62 mN / m or more.
The dynamic surface tension can be measured using a dynamic surface tension meter (SITA science line t60, manufactured by SITA) using an emulsion adjusted to a solid content concentration of 20% by mass at 25 ° C. and 10 Hz. .

As the above-mentioned emulsifier, one kind or two or more kinds of anionic, cationic, nonionic and amphoteric surfactants and polymer surfactants can be used, but the average added mole number is 10 moles or more. An emulsifier and / or a reactive emulsifier having an oxyalkylene group is preferred.
An emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more is difficult to desorb when adsorbed on emulsion particles due to having a long oxyalkylene group, and a reactive emulsifier is a heavy component that forms an emulsion. Since they are bonded to the coalescence, both can exhibit high resilience stability. When such an emulsifier is used, an emulsion having the dynamic surface tension as described above can be produced.
The average added mole number of the oxyalkylene group of the emulsifier having an oxyalkylene group is more preferably 12 moles or more, and still more preferably 15 moles or more. Any emulsifier can be suitably used as long as the average added mole number of the oxyalkylene group is not less than the above value, but the average added mole number of the oxyalkylene group should be 80 moles or less. Is preferred.

The emulsifier is preferably a nonionic surfactant and / or a sulfate ester type anionic surfactant.
That is, in the present invention, the emulsion contained in the coating resin composition was obtained using a nonionic surfactant and / or a sulfate ester type anionic surfactant as an emulsifier when the monomer component was emulsion polymerized. It is preferable.

As an emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene oleyl ether sulfate sodium salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene ( Mono, di, tri) styryl phenyl ether sulfate, polyoxyalkylene (mono, di, tri) benzyl phenyl ether sulfate, polyoxyalkyl ether sulfate, polyoxyethylene carboxylic ester sulfate, polyoxy Ethylene phenyl ether sulfate ester salt, polyoxyethylene alkyl aryl sulfate salt, polyoxyethylene alkyl ether sulfate salt (for example, “ADEKA Rear soap SR-20 "), polyoxyethylene oleyl cetyl ether sulfate (for example," Hitenol W-2320 "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene lauryl ether sulfate (for example, Daiichi Kogyo Seiyaku Co., Ltd.) Sulfuric acid ester type anionic surfactants such as “Hitenol LA-10” manufactured by the Company; polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan aliphatic ester; polyoxyethylene oxypropylene copolymer Nonionic surfactants such as allyloxymethylalkoxyethylhydroxypolyoxyethylene (for example, “ADEKA rear soap ER-20” manufactured by ADEKA), polyoxyalkylene alkenyl ether (for example, “Latemul PD-420” manufactured by Kao Corporation) " Nonionic surfactants having a reactive property such as "LATEMUL PD-430", etc.).

As the reactive emulsifier, among the nonionic surfactants, reactive nonionic surfactants can be used.
1 type may be used for the said emulsifier and 2 or more types may be used for it.

Although the usage-amount of the said emulsifier is 1-3 mass% with respect to 100 mass% of all the monomer components containing the monomer which has an acid group, it is preferable that it is 1.5-3 mass%. More preferably, it is 2-3 mass%.

The emulsion in the present invention may be formed by one kind of polymer or may be formed by two or more kinds of polymers. When it is formed by two or more kinds of polymers, (1) a form obtained by mixing (blending) the obtained emulsion after separately polymerizing and synthesizing, and (2) a series of The form which is a mixture obtained by manufacturing what contains two types of polymers in a manufacturing process (for example, multistage polymerization etc.) is mentioned. In order to obtain what contains two types of polymers in a series of manufacturing processes, it can obtain by setting manufacturing conditions, such as monomer dropping conditions, suitably.

The thing of the form of said (2) is preferable that it is a form of the emulsion particle | grains which have a core part and a shell part. When the emulsion in the present invention is in the form of emulsion particles having a core part and a shell part, the core part and the shell part may be completely compatible with each other and may have a homogeneous structure in which they cannot be distinguished. May be a core-shell composite structure or a microdomain structure that is not completely compatible but formed inhomogeneously.
Among these structures, a core / shell composite structure is preferable in order to sufficiently draw out the characteristics of the emulsion and produce a stable emulsion.
In the core / shell composite structure, the surface of the core part is preferably covered with the shell part. In this case, it is preferable that the surface of the core part is completely covered with the shell part, but it may not be completely covered. For example, the core part may be covered in a mesh shape or in some places. The part may be exposed.
The polymer that forms the core part and the polymer that forms the shell part are, for example, weight average molecular weight, glass transition temperature, SP value (solubility coefficient), type of monomer used, What is necessary is just to be different in any of various physical properties, such as a usage rate.

The emulsion preferably has an average particle diameter of emulsion particles of 100 to 450 nm.
When emulsion particles having an average particle diameter in this range are used, the resin composition for coating can be made excellent in basic performance such as heat drying property and coating property. The upper limit is more preferably 400 nm. More preferably, it is 350 nm. When the average particle diameter of the emulsion particles is within such a range, these functions and effects are more effectively exhibited.
For example, after the emulsion is diluted with distilled water and sufficiently stirred and mixed, about 10 ml of the average particle size (volume average particle size) is collected in a glass cell, and this is measured by a particle size distribution analyzer (Particle Sizing) by dynamic light scattering. It can be determined by measuring with "NICOMP Model 380" manufactured by Systems.

The emulsion particles having the above average particle diameter preferably have a particle size distribution defined by a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter × 100) of 40% or less. More preferably, it is 30% or less. If the particle size distribution exceeds 40%, the width of the particle size distribution of the emulsion particles becomes very wide and some of the particles contain coarse particles. Therefore, the resin composition is sufficient due to the influence of such coarse particles. There is a risk that the heat drying property is not sufficient.

In the present invention, the emulsion is obtained by using 1 to 3% by mass of an emulsifier with respect to 100% by mass of all monomer components including the monomer having an acid group, and has a dynamic surface tension as described above. If it is a thing, the outstanding mechanical stability will be obtained by setting it as the composition containing the said emulsion and a sulfonate type surfactant. Therefore, in order to make the resin composition for coatings excellent in mechanical stability, the glass transition temperature (Tg) of the polymer forming the emulsion is not particularly limited, and a polymer having any glass transition temperature is used. However, the effect of making the resin composition for coatings excellent in mechanical stability can be obtained.
The glass transition temperature (Tg) may be determined based on, for example, already obtained knowledge, or may be controlled by the types and use ratios of the monomer components described later. It can be calculated from the following calculation formula (1).

In the formula, Tg ′ is Tg (absolute temperature) of the polymer. W ₁ ′, W ₂ ′,... Wn ′ are mass fractions of the respective monomers with respect to the total monomer components. T ₁ , T ₂ ,... Tn are glass transition temperatures (absolute temperatures) of homopolymers (homopolymers) composed of the respective monomer components.

Similar to the glass transition temperature of the polymer forming the emulsion, the weight average molecular weight of the polymer forming the emulsion is not particularly limited in order to make the resin composition for coatings excellent in mechanical stability. Even when any weight average molecular weight is used, it is possible to obtain an effect of making the resin composition for coatings excellent in mechanical stability.

As content of the emulsion in the resin composition for coating materials of this invention, it is preferable that solid content of an emulsion is 40-80 mass% with respect to 100 mass% of the whole resin composition. More preferably, it is 50-80 mass%, More preferably, it is 50-70 mass%. In addition, solid content (nonvolatile content) of an emulsion means parts other than a solvent among emulsions.

The resin composition for coatings of the present invention is obtained using 1 to 3% by mass of an emulsifier with respect to 100% by mass of all monomer components including an acid group-containing monomer, at 25 ° C., 10 Hz, solid content An emulsion having a dynamic surface tension of 60 mN / m or more under the condition of 20% by mass, that is, when the emulsion in the present invention and other emulsions are included, the other emulsions include urethane resin, SBR resin, epoxy resin, acetic acid Examples thereof include one or more emulsion resins such as vinyl resins, vinyl chloride resins, vinyl chloride-ethylene resins, vinylidene chloride resins, styrene-butadiene resins, and acrylonitrile-butadiene resins.
The mass ratio of the emulsion in the present invention to the other emulsion (emulsion in the present invention / other emulsion) is preferably 100 to 50/0 to 50.

The resin composition for coatings of this invention contains a sulfonate type surfactant with the said emulsion. The resin composition can be made extremely excellent in mechanical stability by combining a sulfonate type surfactant with the emulsion having high stability as the particles as described above.
The sulfonate-type surfactant contained in the coating resin composition of the present invention is preferably one having no alkylene oxide structure in the structure. When a sulfonate surfactant having no alkylene oxide structure is used, the resin composition can be made more excellent in mechanical stability.
Thus, it is also one of the preferred embodiments of the present invention that the sulfonate type surfactant does not have an alkylene oxide structure in the structure, that is, is a non-oxyalkylene type.

Examples of the sulfonate type surfactant include alkyl sulfonate, α-olefin sulfonate, alkyl benzene sulfonate (for example, “Neopelex G-65” manufactured by Kao Corporation), alkyl diphenyl ether disulfonate (for example, One or two or more kinds of salts such as “Perex SS-H” manufactured by Kao Corporation), alkyl naphthalene sulfonate, dialkyl sulfosuccinate, β-naphthalene sulfonic acid formalin condensate can be suitably used.

The blending ratio of the sulfonate surfactant is preferably 1 to 5% by mass with respect to 100% by mass of the entire coating resin composition. When the amount is less than 1% by mass, the effect of adding the sulfonate surfactant cannot be sufficiently exerted, and when the amount exceeds 5% by mass, physical properties such as a decrease in water resistance of the coating film occur. There is a fear. More preferably, it is 1-4 mass% with respect to 100 mass% of the whole resin composition for coating materials, More preferably, it is 1-3 mass%.

The coating resin composition of the present invention is excellent in mechanical stability, excellent in handling properties, workability during coating, storage properties, and the like. The mechanical stability of the coating composition is preferably such that the agglomeration rate by a Marlon stability test under the following measurement conditions is 0 to 0.01%. With such an agglomeration rate, it can be said that the coating resin composition has sufficient mechanical stability. In addition, the mechanical stability of the paint containing the resin composition for paint can also be measured in the same manner.
<Marlon stability test>
The aggregation rate of the emulsion is measured according to the description of “JIS K6828 (1996) 5.8 mechanical stability” using a Marlon test stability tester (catalog No. 2312-I) manufactured by Kumagai Riki Kogyo Co., Ltd. Sample amount 100g, disc rotation speed 1000rpm / load, load 10kg, measurement time 10min, measurement temperature 25 ° C, filtration before and after measurement uses 100 mesh wire mesh, drying after measurement is 30 minutes at 100 ° C Do. The aggregation rate is calculated by the following formula.
Aggregation rate (%) = {(Dry weight of wire mesh after measurement− (Dry weight of wire mesh before measurement)} / (Sample weight) × 100

Although it does not specifically limit as pH of the emulsion which the resin composition for coating materials of this invention contains, and the resin composition for coating materials, For example, it is preferable that it is 2-10, More preferably, it is 3-9. More preferably, it is 7-8. The pH of the resin composition can be adjusted by adding ammonia water, water-soluble amines, aqueous alkali hydroxide solution, or the like to the resin composition.
In this specification, pH can be measured with a pH meter. It is preferable to measure the value at 25 ° C. using a pH meter (“F-23” manufactured by Horiba, Ltd.).

Although it does not specifically limit as the viscosity of the emulsion which the resin composition for coating materials of this invention contains, and the resin composition for coating materials, For example, it is preferable that it is 1-10000 mPa * s, More preferably, it is 5-1000 mPa * s. More preferably, it is 5 to 500 mPa · s.
The viscosity can be measured using a B-type rotational viscometer under the conditions of 25 ° C. and 20 rpm.

The resin composition for coatings according to the present invention is obtained by emulsifying and polymerizing an emulsion by using 1 to 3% by mass of an emulsifier with respect to 100% by mass of all monomer components including a monomer having an acid group. It is obtained by adding a sulfonate type surfactant to the obtained emulsion. Here, the emulsifier used is not particularly limited as long as the resulting emulsion has a dynamic surface tension of 60 mN / m or more at 25 ° C., 10 Hz, and a solid content of 20% by mass. By using an emulsifier and / or a reactive emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more as an emulsifier at the time of polymerization, the resulting emulsion becomes more excellent in hydration stability. It is preferable to use an emulsifier. When a sulfonate surfactant is added to an emulsion obtained using these emulsifiers, the resulting composition is extremely excellent in mechanical stability. Therefore, such a method for producing a coating resin composition is a preferred method for producing the coating resin composition of the present invention, and this is also one aspect of the present invention.
That is, a method for producing a coating resin composition containing an emulsion obtained by emulsion polymerization of a monomer component, wherein the production method is based on a monomer component containing an acid group-containing monomer. A step of synthesizing an emulsion by using an emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more and / or a reactive emulsifier, and an emulsion obtained by the emulsion polymerization, and a sulfonate A method for producing a resin composition for paints comprising a step of adding a mold surfactant is also one aspect of the present invention.

As a method for producing an emulsion contained in the resin composition for coatings of the present invention, the monomer component is polymerized by an emulsion polymerization method in the presence of an emulsifier, but the form for carrying out the emulsion polymerization is not particularly limited, For example, the polymerization can be carried out by appropriately adding a monomer component, a polymerization initiator and an emulsifier to an aqueous medium for polymerization. Moreover, it is preferable to use a polymerization chain transfer agent or the like for molecular weight adjustment.

When the emulsion which the resin composition for coatings of this invention contains is an emulsion which has a core part and a shell part, it is preferable to obtain using a normal emulsion polymerization method. Specifically, in the presence of an emulsifier, the monomer component is emulsion-polymerized in an aqueous medium to form a core portion, and then the monomer component is further emulsion-polymerized into an emulsion containing the core portion to form a shell portion. It is preferable to obtain by the multistage polymerization to form. As described above, the emulsion contained in the coating resin composition of the present invention is an emulsion having a core part and a shell part, and the emulsion is obtained by multistage polymerization which forms a shell part after the core part is formed. Is also one of the preferred embodiments of the present invention.

The aqueous medium is not particularly limited. For example, water, one or two or more mixed solvents that can be mixed with water, and a mixed solvent in which water is a main component in such a solvent. Etc. Among these, it is preferable to use water.

The polymerization initiator is not particularly limited as long as it is a substance that decomposes by heat and generates radical molecules, but a water-soluble initiator is preferably used. For example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid) Thermal decomposition initiators such as hydrogen peroxide; hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and Rongalite, potassium persulfate and metal salts, redox polymerization of ammonium persulfate and sodium bisulfite, etc. An agent etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The amount of the polymerization initiator used is not particularly limited and may be set as appropriate according to the type of the polymerization initiator. For example, the total amount of monomer components used to form the emulsion is 100 parts by weight. On the other hand, it is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1 part by weight.

In order to promote emulsion polymerization, the polymerization initiator can be used in combination with a reducing agent as necessary. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; for example, reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. These 1 type (s) or 2 or more types can be used.
It does not specifically limit as the usage-amount of the said reducing agent, For example, it is preferable that it is 0.05-1 weight part with respect to 100 weight part of total amounts of the monomer component used in forming an emulsion.

The polymerization chain transfer agent is not particularly limited, for example, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan; carbon tetrachloride , Halogenated hydrocarbons such as carbon tetrabromide and ethylene bromide; mercaptocarboxylic acid alkyl esters such as mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopyropionic acid tridecyl ester; mercaptoacetic acid methoxybutyl Mercaptocarboxylic acid alkoxyalkyl ester such as ester, mercaptopropionic acid methoxybutyl ester; carboxylic acid mercaptoal such as octanoic acid 2-mercaptoethyl ester Glycol ester or, alpha-methylstyrene dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, dipentene, anisole, allyl alcohol and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan. The amount of the polymerization chain transfer agent used is usually 2.0 parts by weight or less, preferably 1.0 part by weight or less, with respect to 100 parts by weight of all monomer components.

The emulsion polymerization may be performed in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as sodium polyacrylate, an inorganic salt, or the like, if necessary. Moreover, as addition methods, such as a monomer component and a polymerization initiator, methods, such as a batch addition method, a continuous addition method, a multistage addition method, are applicable, for example. Moreover, you may combine these addition methods suitably.

Regarding the emulsion polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is preferably 0 to 100 ° C., and more preferably 40 to 95 ° C., for example. Also, the polymerization time is not particularly limited, and for example, it is preferably 1 to 15 hours, and more preferably 5 to 10 hours.
Moreover, it does not specifically limit as addition methods, such as a monomer component and a polymerization initiator, For example, methods, such as a batch addition method, a continuous addition method, a multistage addition method, are applicable. Moreover, you may combine these addition methods suitably.

In the method for producing an emulsion contained in the resin composition for paints of the present invention, it is preferable to produce an emulsion by emulsion polymerization and then neutralize the emulsion with a neutralizing agent. As a result, the emulsion is stabilized. The neutralizing agent is not particularly limited, and for example, triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N- (β-aminoethyl) ethanolamine, diglycolamine, monoethanolamine, 2-hydroxyethylpiperidine. Benzylamine, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) isopropanol, 1,6-hexamethylenediamine; aqueous ammonia; sodium hydroxide and the like can be used. These may be used alone or in combination of two or more.

The coating resin composition of the present invention can form a coating composition together with other components such as pigments. The resin composition for coatings of the present invention is excellent in mechanical stability as described above, and even when a pigment is blended, aggregation of emulsion and pigment particles is effectively suppressed. It can be said that the effect of using the coating resin composition of the present invention is more remarkably exhibited when the coating resin composition and the pigment are combined.
When the pigment is blended, the mass ratio of the coating resin composition to the pigment is preferably 1/1 to 1/3.
Thus, the coating composition containing the coating resin composition of the present invention and the pigment at a mass ratio of 1/1 to 1/3 is also one aspect of the present invention.
Moreover, the coating material containing such a coating composition is also one of this invention.

Further, the effect of effectively suppressing the aggregation of the emulsion and pigment particles as described above is such that the solid content of the coating composition is 70% by mass or more, and the solid content concentration is high and the composition is more likely to aggregate. It can be said that it is more prominent in the case of things.
Thus, it is one of the suitable embodiment of this invention that the solid content concentration of the composition for coatings of this invention is 70 mass% or more.
In addition, solid content concentration means components other than the solvent which the composition for coating materials contains here.

Examples of the pigment include organic or inorganic colorants such as titanium oxide, carbon black, dial, Hansa yellow, benzine yellow, phthalocyanine blue, quinacridone red, metal phosphates, metal molybdates, and metal borate. And other anticorrosive pigments. Among these, inorganic pigments are preferable.

The pigment preferably has a particle size of 1 to 150 μm. Those having such a small particle size are poor in stability and tend to aggregate, but when used in combination with the resin composition for coatings of the present invention, aggregation is suppressed and the coating has excellent mechanical stability. Composition. Therefore, it can be said that the form using the pigment having such a particle size is one of the preferred forms of the coating composition of the present invention.

The coating composition of the present invention can contain a thickener in addition to the pigment.
Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. As a compounding quantity of a thickener, it is preferable to set it as 0.01-2 weight part with solid content with respect to 100 weight part of solid content of the composition for coating materials. More preferably, it is 0.05-1.5 weight part, More preferably, it is 0.1-1 weight part.

Other components that can be blended in the coating composition of the present invention include, for example, a solvent; a plasticizer; a stabilizer; a wetting agent; an antiseptic; an antifoaming agent; a filler; One type or two or more types of anti-aging agents, antifungal agents, ultraviolet absorbers, antistatic agents and the like can be used.
In addition, the said other component can be mixed with the said composition for coating materials etc. using a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver etc., for example.

Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and the like. What is necessary is just to set suitably as a compounding quantity of a solvent so that the solid content density | concentration of the composition for coatings may become the range mentioned above.

Examples of the aqueous crosslinking agent include oxazoline compounds such as Epocross WS-500, WS-700, K-2010, 2020, 2030 (all trade names, manufactured by Nippon Shokubai Co., Ltd.); Adeka Resin EMN-26-60, EM- Epoxy compounds such as 101-50 (both trade names, manufactured by ADEKA); Melamine compounds such as Cymel C-325 (trade names, manufactured by Mitsui Cytec); Block isocyanate compounds; AZO-50 (trade names, 50 Zinc oxide compounds such as a mass% zinc oxide aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd.) are suitable. As a compounding quantity of a water-system crosslinking agent, it is preferable to set it as 0.01-20 weight part by solid content with respect to 100 weight part of solid content of a coating composition, for example, More preferably, it is 0.15-15 weight Parts, more preferably 0.5 to 15 parts by weight.

Examples of the filler include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide, glass talk, magnesium carbonate, aluminum hydroxide, talc, diatomaceous earth, and clay; Examples of the inorganic filler include glass flakes and mica; and fibrous inorganic fillers such as metal oxide whiskers and glass fibers. As a compounding quantity of an inorganic filler, it is preferable to set it as 50-700 weight part with respect to 100 weight part of solid content of the composition for coating materials. More preferably, it is 100-550 weight part.

Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
Examples of the antifoaming agent include silicon-based antifoaming agents.

As the other component, a polyvalent metal compound may be further used.
The form of the polyvalent metal compound may be, for example, a powder, an aqueous dispersion, an emulsion dispersion, or the like. Especially, since the dispersibility in the coating composition improves, it is preferably used in the form of an aqueous dispersion or an emulsified dispersion, and more preferably in the form of an emulsified dispersion. Moreover, it is preferable that the usage-amount of a polyvalent metal compound shall be 0.05-5.0 weight part with respect to 100 weight part of solid content in the composition for coating materials. More preferably, it is 0.05-3.5 weight part.

For example, the coating composition is applied to a substrate and dried to form a coating film. The substrate is not particularly limited. Moreover, as a method of applying the coating composition to the substrate, it can be applied using, for example, a brush, a spatula, an air spray, an airless spray, a mortar gun, a ricin gun or the like.

The coating resin composition of the present invention has the above-described structure, and is a coating resin composition with excellent mechanical stability in which solids aggregation is sufficiently suppressed. Therefore, the solid content concentration is increased. It can be suitably used as a resin composition for forming a coating composition having excellent storage properties and workability during coating.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following production examples and examples, various physical properties and the like were evaluated as follows.
<Nonvolatile content (N.V.)>
About 1 g of the obtained aqueous resin dispersion was weighed, and after 110 hours at 110 ° C. with a hot air drier, the remaining amount after drying was regarded as a non-volatile content, and the ratio to the mass before drying was expressed in mass%.
<PH>
The value at 25 ° C. was measured with a pH meter (“F-23” manufactured by Horiba, Ltd.).
<Viscosity>
Using a B-type rotational viscometer, the measurement was performed at 25 ° C. and 20 rpm.

<Average particle size, particle size distribution>
The volume average particle diameter was measured using a particle size distribution measuring apparatus (“NICOMP Model 380” manufactured by Particle Sizing Systems) by a dynamic light scattering method.
Further, a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter × 100) was calculated as the particle size distribution.

<Glass transition temperature (Tg)>
It calculated using the following formula (1) from the monomer composition.

In addition, Tg calculated from the monomer composition used in all stages was described as “total Tg”.
The Tg values of the respective homopolymers used to calculate the glass transition temperature (Tg) of the polymerizable monomer component by the above calculation formula (1) are shown below.
Methyl methacrylate (MMA): 105 ° C
Styrene (St): 100 ° C
Butyl acrylate (BA): -56 ° C
2-ethylhexyl acrylate (2EHA): -70 ° C
Acrylic acid (AA): 95 ° C

<Dynamic surface tension>
Using a dynamic surface tension meter (SITA science line t60, manufactured by SITA), an emulsion adjusted to a solid content concentration of 20% by mass was measured under the conditions of 25 ° C. and 10 Hz.
<Mechanical stability (coagulation rate)>
The aggregation rate of the emulsion is measured according to the description of “JIS K6828 (1996) 5.8 mechanical stability” using a Marlon test stability tester (catalog No. 2312-I) manufactured by Kumagai Riki Kogyo Co., Ltd. Sample amount 100g, disc rotation speed 1000rpm / load, load 10kg, measurement time 10min, measurement temperature 25 ° C, filtration before and after measurement uses 100 mesh wire mesh, drying after measurement is 30 minutes at 100 ° C Do. The aggregation rate was calculated by the following formula.
Aggregation rate (%) = {(Dry weight of wire mesh after measurement− (Dry weight of wire mesh before measurement)} / (Sample weight) × 100

Production Example 1
300 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 305 parts of styrene, 205 parts of methyl methacrylate, 190 parts of 2-ethylhexyl acrylate, 290 parts of butyl acrylate, 15 parts of acrylic acid, and Hightenol W-2320 previously adjusted to a 20% aqueous solution (trade name, No. 1 A monomer emulsion consisting of 100.0 parts (manufactured by Kogyo Seiyaku Co., Ltd.) and 274 parts deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 10 parts of the above monomer emulsion, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogensulfite aqueous solution were added, Polymerization was performed. After the initial polymerization, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 100 parts of a 5% potassium persulfate aqueous solution and 100 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 180 minutes, and the same temperature was maintained for 60 minutes after completion of the addition. After cooling the resulting reaction liquid to room temperature, 12 parts of diglycolamine was added to obtain an emulsion having a non-volatile content of 55%, pH 8.0, viscosity of 420 mPa · s, average particle size of 230 nm, particle size distribution of 22%, and Tg of 0 ° C. It was.

Production Example 2
300 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. -On the other hand, in the above dropping funnel, 305 parts of styrene, 205 parts of methyl methacrylate, 190 parts of 2-ethylhexyl acrylate, 290 parts of butyl acrylate, 15 parts of acrylic acid, Haitenol LA-10 previously adjusted to a 20% aqueous solution (trade name) (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A monomer emulsion consisting of 100.0 parts and 274 parts of deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 10 parts of the above monomer emulsion, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogensulfite aqueous solution were added, Polymerization was performed. After the initial polymerization, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 100 parts of a 5% potassium persulfate aqueous solution and 100 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 180 minutes, and the same temperature was maintained for 60 minutes after completion of the addition. After cooling the resulting reaction solution to room temperature, 12 parts of diglycolamine was added, and a non-volatile content 55%, pH 8.2, viscosity 320 mPa · s, average particle size 200 nm, particle size distribution 25%, Tg 0 ° C. Obtained.

Production Example 3
300 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 305 parts of styrene, 205 parts of methyl methacrylate, 190 parts of 2-ethylhexyl acrylate, 290 parts of butyl acrylate, 15 parts of acrylic acid, and Adekaria soap SR-20 (trade name, ADEKA previously adjusted to 20% aqueous solution) A monomer emulsion consisting of 100.0 parts) and 274 parts deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 10 parts of the above monomer emulsion, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogensulfite aqueous solution were added, Polymerization was performed. After the initial polymerization, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 100 parts of a 5% potassium persulfate aqueous solution and 100 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 180 minutes, and the same temperature was maintained for 60 minutes after completion of the addition. After cooling the obtained reaction liquid to room temperature, 12 parts of diglycolamine was added to obtain an emulsion having a nonvolatile content of 55%, pH 8.1, viscosity of 220 mPa · s, average particle size of 240 nm, particle size distribution of 24%, and Tg of 0 ° C. It was.

Production Example 4
300 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 305 parts of styrene, 220 parts of methyl methacrylate, 190 parts of 2-ethylhexyl acrylate, 290 parts of butyl acrylate, and Haitenol W-2320 (trade name, Daiichi Kogyo Seiyaku Co., Ltd.) previously adjusted to a 20% aqueous solution were added to the dropping funnel. (Manufactured) A monomer emulsion consisting of 100.0 parts and 274 parts of deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 10 parts of the above monomer emulsion, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogensulfite aqueous solution were added, Polymerization was performed. After the initial polymerization, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 100 parts of a 5% potassium persulfate aqueous solution and 100 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 180 minutes, and the same temperature was maintained for 60 minutes after completion of the addition. After cooling the resulting reaction solution to room temperature, 0.5 part of diglycolamine is added, and an emulsion having a non-volatile content of 55%, pH 8.0, viscosity of 220 mPa · s, average particle size of 280 nm, particle size distribution of 28%, and Tg of 0 ° C. Got.

Production Example 5
300 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 305 parts of styrene, 220 parts of methyl methacrylate, 190 parts of 2-ethylhexyl acrylate, 290 parts of butyl acrylate, ADEKA rear soap SR-20 (trade name, manufactured by ADEKA) 100 previously adjusted to a 20% aqueous solution in the above dropping funnel 100 A monomer emulsion consisting of 0.0 part and 274 parts deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 10 parts of the above monomer emulsion, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogensulfite aqueous solution were added, Polymerization was performed. After the initial polymerization, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. At the same time, 100 parts of a 5% potassium persulfate aqueous solution and 100 parts of a 2% sodium hydrogensulfite aqueous solution were uniformly added dropwise over 180 minutes, and the same temperature was maintained for 60 minutes after completion of the addition. After cooling the obtained reaction liquid to room temperature, 0.5 part of diglycolamine is added, and an emulsion having 55% non-volatile content, pH 8.3, viscosity 190 mPa · s, average particle size 260 nm, particle size distribution 24%, Tg 0 ° C. Got.

Resin composition 1
7.5 parts of Neoperex G-65 (manufactured by Kao Corporation) diluted to 20% was added to 100 parts of the emulsion of Production Example 1 to prepare Resin Composition 1.

Resin composition 2
7.5 parts of Neoperex G-65 (manufactured by Kao Corporation) diluted to 20% was added to 100 parts of the emulsion of Production Example 3 to prepare Resin Composition 2.

Resin composition 3
7.5 parts of Perex SS-H (manufactured by Kao Corporation) diluted to 20% was added to 100 parts of the emulsion of Production Example 1 to prepare Resin Composition 3.

Resin composition 4
7.5 parts of Hightenol W-2320 (Daiichi Kogyo Seiyaku Co., Ltd.) diluted to 20% was added to 100 parts of the emulsion of Production Example 1 to prepare Resin Composition 4.

Resin compositions 5-8
The emulsion of Production Example 1 was designated as Resin Composition 5. Similarly, the emulsion of Production Example 2 was designated as Resin Composition 6, the emulsion of Production Example 4 as Resin Composition 7, and the emulsion of Production Example 5 as Resin Composition 8.

Examples 1-5, Comparative Examples 1-5
The dynamic surface tension of the emulsions of Production Examples 1 to 5 and the mechanical stability (Marlon aggregation rate) of the resin compositions 1 to 8 were measured. The results are shown in Table 1.
Moreover, the coating materials were prepared by the compounding shown in Table 1 using the resin compositions 1-8. Formulations 1-3 are as shown below. In addition, the same thing as the mixing | blending 1 was used for the dispersing agent, antifoamer, and thickener in the mixing | blending 2 and 3.
The prepared paint was also measured for mechanical stability (Marlon aggregation rate). The results are shown in Table 1.

Formula 1
Resin composition 100 parts Calcium carbonate NN # 200 ^{* 1} 200 parts Dispersant AQUARIDC DC-40S ^{* 2} 0.5 parts Antifoam Nopco 8034L ^{* 3} 0.5 parts Thickener Acryset WR-503A ^{* 4} 1 part Ion exchange Water 30 parts * 1: Nitto Flour & Chemical Co., Ltd. filler * 2: Nippon Shokubai Co., Ltd. polycarboxylic acid type dispersant (active ingredient 44%)
* 3: Nippon Shokubai Co., Ltd. Alkali-soluble acrylic thickener (active ingredient 30%)
* 4: Defoaming agent manufactured by San Nopco Co., Ltd. (main component: hydrophobic silicone + mineral oil)

Formula 2
Resin composition 100 parts Calcium carbonate 100 parts Dispersant 0.5 parts Antifoaming agent 0.5 parts Thickener 1 part

Formula 3
Resin composition 100 parts Calcium carbonate 50 parts Dispersant 0.5 parts Antifoaming agent 0.5 parts Thickener 2 parts Ion-exchanged water 50 parts

From the results of Examples and Comparative Examples, an emulsion obtained from a monomer component having an acid group using an emulsifier having a dynamic surface tension of 60 mN / m or more at 25 ° C., 10 Hz, and a solid content of 20% by mass; It was confirmed that the resin composition containing the sulfonate surfactant and the paint obtained using this resin composition are excellent in mechanical stability. In the examples, a specific emulsifier, a monomer component as a raw material of the emulsion, and a sulfonate type surfactant are used, but the dynamic surface tension at a solid content of 20% by mass is 60 mN / m. Since the mechanism that exhibits excellent mechanical stability when combining an emulsion obtained from a monomer component having an acid group with the above emulsifier and a sulfonate type surfactant is the same, From the results of the above-mentioned Examples and Comparative Examples, it can be said that the present invention can be applied in various forms disclosed in the present specification and can exhibit advantageous effects.

Claims (7)

A method for producing a resin composition for coatings containing an emulsion obtained by emulsion polymerization of a monomer component,
The emulsion is obtained using 1 to 3% by mass of an emulsifier with respect to 100% by mass of all monomer components including a monomer having an acid group,
The emulsifier is an emulsifier and / or reactive emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more,
The dynamic surface tension under the conditions of 25 ° C., 10 Hz, solid content of 20% by mass is 60 mN / m or more,
The manufacturing method is a manufacturing method of the coating resin composition characterized <br/> comprises a step of adding a sulfonate surfactant to the emulsion. The method for producing a coating resin composition according to claim 1, wherein the emulsion is an acrylic emulsion. The method for producing a coating resin composition according to claim 1 or 2, wherein the emulsifier is a nonionic surfactant and / or a sulfate ester type anionic surfactant. The method for producing a coating resin composition according to any one of claims 1 to 3, wherein the sulfonate surfactant is a non-oxyalkylene type. The resin composition for paints according to any one of claims 1 to 4, wherein the sulfonate type surfactant is added in an amount of 1 to 5% by mass with respect to 100% by mass of the resin composition for paints as a whole. Manufacturing method . A method for producing a resin composition for coatings containing an emulsion obtained by emulsion polymerization of a monomer component,
The production method comprises subjecting a monomer component containing an acid group-containing monomer to emulsion polymerization using an emulsifier and / or reactive emulsifier having an oxyalkylene group having an average addition mole number of 10 mol or more. The manufacturing method of the resin composition for coating materials characterized by including the process of synthesize | combining an emulsion, and the process of adding a sulfonate-type surfactant with respect to the emulsion obtained by this emulsion polymerization. It includes a step of mixing the paint resin composition obtained by the method for producing a paint resin composition according to any one of claims 1 to 6 and a pigment at a mass ratio of 1/1 to 1/3. A method for producing a coating composition.