JP2001342201A - Method of producing resin emulsion, coating composition, and its coating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a resin emulsion, capable of intentionally controlling particle size distribution, capable of preventing agglomerates from generating, and therefore capable of practically producing the resin emulsion which has the particle size distribution spreading to a wide range, even when a one-step emulsion polymerization process is applied to the method by the use of a vinyl-based monomer, to provide a coating composition given by using the obtained resin emulsion, and to provide a coating method for coating the composition. SOLUTION: This method of producing the resin emulsion comprises subjecting the vinyl-based monomer to emulsion polymerization in an aqueous medium into which an electrolytic material is dissolved, while decreasing a concentration of the electrolytic material, and further, preferably, while increasing activity brought about a surfactant. The coating composition contains the obtained resin emulsion. Further, the coating method comprises coating the obtained composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful method for producing a resin emulsion, a coating composition containing the resin emulsion obtained by this method as an essential component, and a coating for applying the coating composition. About the law. More specifically, the present invention relates to a method for producing a resin emulsion in which a vinyl monomer is emulsion-polymerized while reducing the concentration of the electrolyte substance in an aqueous medium in which the electrolyte substance is dissolved. The present invention relates to a coating composition containing the obtained resin emulsion as an essential component, and a coating method for coating the coating composition.

[0002]

2. Description of the Related Art There have been many reports on a method for producing a resin emulsion by an emulsion polymerization method. Further, in recent years, a method for producing a high-concentration resin emulsion by a two-stage emulsion polymerization method has been proposed for the purpose of quick drying of a coating film, pursuit of a higher finish appearance, and reduction of distribution costs (Japanese Patent Application Laid-Open No. 60-179402). Gazette). However, in such a production method, the process is complicated and the reaction time becomes long, and it cannot be said that it is still insufficient to produce a resin emulsion having a high nonvolatile content and a low viscosity on a practical production scale. In a one-stage emulsion polymerization method using a vinyl monomer,
A method for producing a resin emulsion that satisfies a wide range of required film performances, has a wide particle size distribution on a practical production scale, and minimizes the generation of aggregates has not yet been established. is there. As a result, to design an emulsion that satisfies these characteristics, such as the characteristics such as high non-volatile content and low viscosity, which are highly demanded in recent years, or the various required performances such as quick drying, compatibility between coating properties and film properties. At present, it is not enough.

[0003]

SUMMARY OF THE INVENTION In view of the drawbacks of the emulsion polymerization method, an object of the present invention is to use a vinyl monomer such as a (meth) acrylic acid ester without impairing the stability on a practical scale. A method for producing a resin emulsion in which the particle size distribution can be intentionally controlled, the generation of aggregates can be suppressed, and a resin emulsion with a wide particle size distribution can be produced even by a single-stage emulsion polymerization method. And a coating method for coating the coating composition.

[0004]

In the emulsion polymerization of a resin emulsion, it is generally known to add an electrolyte substance to an aqueous medium for controlling the particle size. When the electrolyte substance was added to the aqueous medium in an amount exceeding the weight%, the polymerization stability was deteriorated, agglomerates were generated frequently, and the solution could not be put to practical use.

However, the inventors of the present invention have conducted intensive studies, and as a result, the vinyl monomer was emulsion-polymerized in an aqueous medium in which the electrolyte substance was dissolved while intentionally lowering the electrolyte substance concentration. Even if the concentration of the electrolyte substance in the aqueous medium at the start of the polymerization is in a range exceeding 1% by weight or emulsion polymerization by a one-step reaction, a practical scale is applicable to a wide range of vinyl monomers. It is possible to control the particle size distribution of the resin emulsion, the balance between the non-volatile content and the viscosity, the amount of formed aggregates, etc. without impairing the polymerization stability, minimize the generation of aggregates, and reduce the particle size. It has been found that a resin emulsion having a remarkably wide distribution and a resin emulsion in which the particle size distribution is intentionally controlled can be produced.

Further, the present inventors have further reduced the concentration of the electrolyte substance in the aqueous medium, and at the same time, increased the surfactant activity while emulsion-polymerizing the vinyl-based monomer. High concentration, low viscosity, and can produce an emulsion in which the generation of aggregates is extremely suppressed, using a water-soluble polymerization initiator as a part or all of the electrolyte material,
The concentration of the electrolyte substance in the aqueous medium at the start of the emulsion polymerization is 1 to 3
% By weight, the electrolyte substance is preferably a persulfate, and the vinyl monomer is (meth)
It is preferable that the concentration of the electrolyte in the aqueous medium be lowered with time by emulsion polymerization while dropwise adding a (meth) acrylic acid ester having one acryloyl group as an essential component. The obtained surfactant is preferably an anionic surfactant, or a mixture of an anionic surfactant and a nonionic surfactant,
It has been found that the resin emulsion thus obtained can be suitably used for a coating composition, and that the obtained coating composition can be used for various coating methods.

That is, the present invention provides: In an aqueous medium in which an electrolyte substance is dissolved, while lowering the concentration of the electrolyte substance, characterized by emulsion-polymerizing a vinyl monomer, a method for producing a resin emulsion,

[0008] 2. The method for producing a resin emulsion according to the above 1, wherein a water-soluble polymerization initiator is used as the electrolyte substance, and the concentration of the electrolyte substance in the aqueous medium at the start of emulsion polymerization of the vinyl monomer is 1 to 3% by weight.

3. The method for producing a resin emulsion according to the above 1 or 2, wherein the electrolyte substance is a persulfate;

[0010] 4. The method for producing a resin emulsion according to the above 1, 2, or 3, wherein the vinyl monomer is emulsion-polymerized while increasing the surfactant activity.

5. The method for producing a resin emulsion according to any one of the above 1 to 4, wherein emulsion polymerization is performed while adding a vinyl monomer emulsified with a surfactant in an aqueous medium in which an electrolyte substance is dissolved,

6. The method for producing a resin emulsion according to claim 4 or 5, wherein the surfactant is an anionic surfactant or a mixture of an anionic surfactant and a nonionic surfactant.

7. The method for producing a resin emulsion according to any one of the above 1 to 6, wherein the vinyl monomer contains, as an essential component, a (meth) acrylic ester having one (meth) acryloyl group.

8. Obtaining the resin emulsion by one-stage emulsion polymerization, the method for producing a resin emulsion according to any one of the above 1 to 7,

9. A coating composition comprising, as an essential component, a resin emulsion obtained by the production method according to any one of the above 1 to 8, and

10. A coating method, characterized by coating the coating composition according to the above item 9.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. In carrying out the method for producing the resin emulsion of the present invention, various emulsion polymerization methods can be used. As the emulsion polymerization method, a method such as a thermal decomposition method using thermal decomposition of a polymerization initiator, a known oxidizing agent and a reducing agent, and if necessary, a redox polymerization method using an acid or a metal ion can also be used.

Next, a specific example of the manufacturing method will be described. Prior to the reaction, a vinyl monomer emulsified with a surfactant, preferably a vinyl monomer containing, as an essential component, a (meth) acrylic ester having one (meth) acryloyl group (hereinafter, this emulsified monomer) The resulting vinyl monomer is abbreviated as “pre-emulsion”.) The pre-emulsion is prepared, for example, by dissolving a surfactant in ion-exchanged water in advance in a stirring vessel, adding a vinyl-based monomer into this, and sufficiently stirring and emulsifying.

Separately, a water-soluble polymerization initiator and, if necessary, a reducing agent are dissolved in ion-exchanged water in a polymerization initiator preparation container.

Next, a reaction vessel for emulsion polymerization equipped with a stirring blade, a thermometer and a reflux condenser is prepared, and an aqueous medium is previously charged. The temperature is raised to the temperature required for the emulsion polymerization reaction, and a small amount of the pre-emulsion is added in order to form initial particles as necessary. If necessary, a surfactant or an emulsion for seeds may be used separately. Next, a required amount of the electrolyte substance and / or the polymerization initiator is charged and stirred to form initial particles as required. It is preferable to set the concentration of the electrolyte substance in the aqueous medium at this time to 1 to 3% by weight. Thereafter, dropping of the pre-emulsion and, if necessary, the polymerization initiator and the reducing agent are started. At that time, the concentration of the electrolyte in the aqueous medium in the reaction vessel decreases as the pre-emulsion, the polymerization initiator, and the dropping rate and the dropping amount of the reducing agent are intentionally adjusted. At this time, it is preferable to increase the emulsifier concentration in parallel. Surprisingly, the particle size of the resulting emulsion changes extremely with time, and in a normal one-stage emulsion polymerization method, a large particle size distribution, a high non-volatile content, a low viscosity It becomes possible to produce an emulsion.

The concentration of the electrolyte substance in the aqueous medium is preferably from 1 to 3% by weight, because the particle size distribution is wide and the balance between the coating suitability and the film physical properties can be satisfied. It is preferable to obtain a resin emulsion which exhibits the performance of a high-concentration emulsion, has good polymerization stability, generates few agglomerates, and can be suitably used practically, and more preferably 1.5 to 2.5% by weight. Is particularly preferred. However, even when the concentration of the electrolyte substance is in the range of 1 to 3% by weight, if emulsion polymerization is performed without decreasing the concentration of the electrolyte over time, a resin emulsion having a wide particle size distribution, a high nonvolatile content, and a low viscosity is obtained. It cannot be manufactured, and the generation of aggregates becomes extremely large, making it unpractical. In addition, the surfactant activity is to gradually increase the surfactant activity in an aqueous medium by emulsion polymerization while adding a pre-emulsion, and to practically use an emulsion having a wider particle size distribution than ever before. Can be manufactured.

When emulsion polymerization of a vinyl monomer is carried out while increasing the surfactant activity, the concentration of the surfactant in the container at the end of the dropping is 1% of the initial concentration of the surfactant in the container.
It is preferable to adjust the surfactant concentration in the pre-emulsion so as to be 0 times or more, and it is particularly preferable to adjust the surfactant concentration so as to be 20 times or more. On the other hand, the vinyl monomer is emulsion-polymerized while simultaneously lowering the electrolyte concentration in the container.

In adjusting the surfactant concentration,
The surfactant concentration in the pre-emulsion is such that it is easy to carry out emulsion polymerization while increasing the surfactant capacity, and a resin emulsion with a wide particle size distribution and good coating properties such as water resistance can be obtained. Therefore, the range is preferably 0.5 to 6% by weight, and particularly preferably 2 to 4% by weight.

The initial electrolyte substance concentration in the aqueous medium may be substantially 0% by weight, and a surfactant may be added. In this case, the surfactant concentration is preferably 0.5% by weight or less, and particularly preferably 0.001 to 0.1% by weight.

When the initial emulsion is formed by charging the pre-emulsion, the amount of the pre-emulsion is determined by the concentration of the surfactant in the aqueous medium at the start of the reaction because a resin emulsion having a wide particle size distribution is obtained. 0.5% by weight or less is preferable, and 0.001 to
Particularly preferred is 0.1% by weight. Even when the surfactant is previously added to the aqueous medium, the total concentration of the surfactant and the surfactant in the pre-emulsion for forming initial particles is 0.5% by weight or less, preferably 0.001 to 0.1% by weight. % Is preferably adjusted.

Further, it does not hinder that the emulsion polymerization is carried out by adding the seed emulsion to the initially charged aqueous medium. In this case, too, the aqueous medium including the amount of the surfactant in the seed emulsion is used. The total surfactant concentration in the solution is 0.5% by weight or less, preferably 0.001 to
It is preferable to adjust so as to be 0.1% by weight.

In the production of the resin emulsion according to the present invention, any known and commonly used vinyl monomer can be used, but if only typical ones are exemplified, Examples of various vinyl monomers shown below are given. These can be used alone or 2
It goes without saying that more than one kind may be used in combination.

Such vinyl monomers include (meth)
(Meth) acrylic acid ester having one acryloyl group [abbreviated as “(meth) acrylic acid ester”) ] Can be suitably used.

Particularly typical examples of the (meth) acrylate include methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
N-octyl acrylate, isooctyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate;

Various alkyl carbitol (meth) acrylates such as ethyl carbitol (meth) acrylate; isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate or dicyclopentenyl Roxyethyl (meth) acrylate;

(Alkoxy) polyalkylene glycol mono (meth) acrylates such as methoxy polyethylene glycol mono (meth) acrylate and ethoxy polyethylene glycol mono (meth) acrylate.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 2
-Hydroxybutyl, 4-hydroxybutyl (meth) acrylate; ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate,
Mono (meth) alkylene glycol such as polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate; monoacrylates of ethylene and propylene mixed ether glycols ) Acrylates; so-called lactone-modified hydroxyl-containing (meth) compounds obtained by subjecting the above-mentioned hydroxyl-containing (meth) acrylic esters to ring-opening reaction with ε-caprolactone.
Acrylate and the like.

Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, itaconic acid, and maleic anhydride; itaconic acid, monoesters of maleic acid and a monoalkyl alcohol having 1 to 8 carbon atoms, and the like. Is mentioned. From the viewpoint of obtaining a resin emulsion having a wide particle size distribution, the carboxyl group-containing vinyl monomer is preferably 3% by weight or less of all vinyl monomers.

Examples of the hydrolyzable silyl group-containing vinyl monomer include, for example, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth)
Acryloyloxypropylmethyldimethoxysilane and the like can be mentioned.

Examples of the vinyl monomer containing an epoxy group include:
For example, glycidyl esters of (meth) acrylic acid such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate;
Alicyclic epoxy group-containing (meth) acrylic acids such as epoxycyclohexyl; (methyl) glycidyl ether of (meth) allyl alcohol, N-glycidylacrylamide, glycidyl vinylsulfonate and the like.

As the fluorine-containing vinyl monomer, for example, trifluoromethyl trifluorovinyl ether,
Perfluoroalkyl perfluorovinyl ether or (per) fluoroalkylvinyl ether (such as pentafluoroethyl trifluorovinyl ether, heptafluoropropyl trifluorovinyl ether), provided that the alkyl group has 1 to 18 carbon atoms. Is mentioned.

Examples of the phosphoric ester group-containing vinyl monomer include mono [(meth) acryloyloxyethyl] phosphate, acidic (meth) acrylic acid ester, and phenyl (meth) acryloyloxyethyl phosphate. .

Sulfonic acid (salt) -containing vinyl monomers include p-styrenesulfonic acid and vinylsulfonic acid;
(Meth) acrylic sulfonic acid, (meth) acryloyloxyethylsulfonic acid; isoprenesulfonic acid; 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like; metal salts such as sodium salt and potassium salt thereof, and ammonium salts and the like Is mentioned.

In the present invention, a surfactant having a polymerizable vinyl group in a molecule, which is generally called a reactive surfactant, can be used as a vinyl monomer simultaneously with the surfactant. Bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate [Antox MS-60 manufactured by Nippon Emulsifier Co., Ltd.], (meth) acryloyloxyalkylene sulfate [Eriminol RS-30 manufactured by Sanyo Chemical Industries, Ltd.] , Polyoxyethylene alkylpropenyl phenyl ether sulfate [AQUALON HS-1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
0, HS-1025], α- [1-[(allyloxy)
Methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypoly (n = 1 to 100) oxyethylene [Adekaria Soap NE-10, NE-2 manufactured by Asahi Denka Kogyo Co., Ltd.]
0, NE-30] and the same sulfate salt [Adekaria Soap SE-10N, SE-102, manufactured by Asahi Denka Kogyo Co., Ltd.]
5N, SE-1025A], alkyl allyl sulfosuccinate [Eleminol JS- manufactured by Sanyo Chemical Industries, Ltd.]
2], sulfosuccinic acid-type reactive activators [Latemul S-180, S-180A manufactured by Kao Corporation] and the like. Here, the salts include metal salts such as sodium salts and potassium salts, ammonium salts and the like.

The aromatic vinyl monomers include styrene, o-vinyltoluene, m-vinyltoluene and p-vinyltoluene.
Aromatic vinyl compounds such as -vinyltoluene, α-methylstyrene, p-tert-butylstyrene, polyfunctional divinylbenzene, trivinylbenzene and the like.

Examples of the amide group-containing vinyl monomer include, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide,
-Iso-propyl (meth) acrylamide, Nn-
Butyl (meth) acrylamide, N-iso-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-amyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-heptyl (meth) acrylamide, N-2-ethylhexyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxy Methyl (meth) acrylamide, Nn-propoxymethyl (meth) acrylamide, N-iso-propoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-iso-butoxymethyl (meth) acrylamide, -Tert-butoxymethyl (meth) acrylamide, N-amyloxymethyl (meth) acrylamide, N-hexyloxy (meth) acrylamide, N-heptyloxymethyl (meth) acrylamide, N-octyloxymethyl (meth) acrylamide, N -2-ethyl-hexyloxymethyl (meth) acrylamide, diacetone (meth) acrylamide and the like.

Examples of the nitrogen-containing vinyl monomer include various dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
tert-butylaminoethyl (meth) acrylate, t
tert-butylaminopropyl (meth) acrylate,
Aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl Oxazoline, (meth) acrylonitrile and the like.

Examples of the quaternary ammonium group-containing vinyl monomer include dimethylaminoethyl methyl chloride (meth) acrylate [Acryester D manufactured by Mitsubishi Rayon Co., Ltd.]
MC], dimethylaminoethyl benzyl chloride (meth) acrylate [Acryester DM160 manufactured by Mitsubishi Rayon Co., Ltd.], hydroxypropyltrimethylammonium chloride (meth) acrylate [Blemmer QA manufactured by NOF Corporation] and the like.

Further, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate,
Vinyl caprylate, vinyl caprate, vinyl laurate, branched (branched) aliphatic carboxylate having 9 carbon atoms, branched (branched) aliphatic carboxylate having 10 carbon atoms, carbon atom Various aliphatic vinyl carboxylate, such as a branched (branched) aliphatic vinyl carboxylate and vinyl stearate represented by Formula 11, vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, p-tert-butyl Various vinyl esters of carboxylic acids having a cyclic structure such as vinyl benzoate; various alkyl vinyl ethers such as ethyl vinyl ether, hydroxyethyl vinyl ether, hydroxy n-butyl vinyl ether, hydroxyisobutyl vinyl ether, cyclohexyl vinyl ether and lauryl vinyl ether. Ethers, and the like.

Examples of the polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. A) alkylene ether di (meth) acrylate such as acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene and propylene mixed ether glycol di (meth) acrylate; 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polyfunctional acrylates such as alkylene oxide adducts thereof; diallyl phthalate, and the like;
These are usually used in combination with a vinyl monomer having one vinyl group.

Examples of the surfactant used in the present invention include various surfactants. Among them, an anionic surfactant or a mixture of an anionic surfactant and a nonionic surfactant is preferable. In particular, an alkyl diphenyl ether disulfonate can be suitably used as the anionic surfactant.

Examples of the alkyl diphenyl ether disulfonate include diammonium dodecyl diphenyl ether disulfonate [Newcol 271NH manufactured by Nippon Emulsifier Co., Ltd.] and disodium dodecyl diphenyl ether disulfonate [Newcol 261A manufactured by Nippon Emulsifier Co., Ltd. Coal 271A, Newcol 271S], dicalcium dodecyl diphenyl ether disulfonate [Newcol 271 manufactured by Nippon Emulsifier Co., Ltd.]
C], sodium alkyl diphenyl ether disulfonate [Perex SSH and SSL manufactured by Kao Corporation, Sandet BL manufactured by Sanyo Chemical Industries, Ltd., Eleminor MON]
-2, Eleminol MON-7]. The alkyldiphenyl ether disulfonate can be used alone or in combination with two or more other anionic surfactants or nonionic surfactants. As the nonionic surfactant, a combination with a polyoxyethylene alkylphenyl ether described below having an HLB of 13.0 or more can be suitably used.

As the surfactant used in the present invention, in addition to the above-mentioned alkyldiphenyl ether disulfonate, various anionic surfactants and nonionic surfactants may be used alone or in combination of two or more. Can be used. As an example of such a surfactant, as the anionic surfactant, an alkylbenzene sulfonate type surfactant such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate;
Alkyl sulfate ester type surfactants such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylate type surfactants such as sodium fatty acids and potassium oleate; sodium polyoxyethylene alkyl ether sulfate and polyoxyethylene alkyl Polyoxyethylene alkyl ether sulfate ester type surfactant such as ammonium ether sulfate; polyoxyethylene alkyl phenyl ether sulfate ester type surfactant such as sodium polyoxyethylene alkyl phenyl ether sulfate and ammonium polyoxyethylene alkyl phenyl ether sulfate Polyoxyethylene such as sodium polyoxyethylene polycyclic phenyl ether sulfate and polyoxyethylene polycyclic phenyl ether ammonium sulfate; Polycyclic phenyl ether sulfate ester type surfactants; Surfactants such as naphthalene sulfonic acid formalin condensate such as sodium naphthalene sulfonic acid condensate; Sodium dialkyl sulfosuccinate and disodium monoalkyl succinate sulfonate Surfactants such as alkyl succinate sulfonates and the like can be mentioned.

The nonionic surfactants used in the present invention include, for example, alkyl ether surfactants such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether; Alkyl phenyl ether surfactants such as ethylene nonyl phenyl ether; alkyl ester surfactants such as polyoxyethylene oleate; alkyl amine surfactants such as polyoxyethylene alkyl amine; sorbitan laurate, polyoxy Surfactants comprising sorbitan derivatives such as ethylene sorbitan laurate and polyoxyethylene sorbitan oleate; polyoxyethylene polycyclic phenyl ether [Emulgen A-50 manufactured by Kao Corporation]
0, A-90, A-60; polycyclic phenyl ether type surfactants such as Newcol 740, 2614 manufactured by Nippon Emulsifier Co., Ltd .; nonionic surfactants in which oxyethylene of these nonionic surfactants is changed to oxyalkylene Surfactants and the like.

The use of a cationic surfactant or a zwitterionic surfactant is not impeded at all, and examples thereof include cationic surfactants such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and alkylbenzylammonium chloride; Zwitterionic surfactants such as alkyl betaines are included. In addition, acetylene-based surfactant [Surfinol SEF manufactured by Air Products Japan Co., Ltd.]
Etc. can be used.

As the electrolyte substance to be added to the aqueous medium, it is preferable to use a persulfate which is a water-soluble polymerization initiator. However, a combination of a persulfate and one or more other electrolyte substances is preferable. Alternatively, a non-electrolytic polymerization initiator and one or more other electrolytic substances are combined to form an aqueous medium having an electrolyte substance concentration of 1 to 3% by weight, preferably 1.5 to 2.5% by weight. It is preferable to use it by adding it so that it becomes% by weight. Further, when using a persulfate as an electrolyte substance, put an aqueous medium into the reaction vessel,
After the temperature is raised to a temperature at which the persulfate can be decomposed, the persulfate may be added. Such a temperature is 75 to 90 ° C. for a thermal decomposition reaction, and 40 to 90 ° C. for a redox polymerization reaction.
~ 80 ° C is usually used.

As the polymerization initiator effective as an electrolyte substance used in the present invention, water-soluble persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate are suitable as described above. Any of various organic / inorganic electrolyte polymerization initiators suitable for emulsion polymerization can be used alone or in combination. Examples of the organic electrolyte polymerization initiator include 2,2'-azobis (2-amidinopropane) dihydrochloride And water-soluble azo compounds such as sodium azobiscyanovalerate, ammonium azobiscyanovalerate and calcium azobiscyanovalerate. Further, as a polymerization initiator capable of emulsion polymerization that can be used in combination with an electrolyte substance, for example, 4,4′-azobis-4-cyanovaleric acid, tert-butyl hydroxide [Perbutyl H manufactured by NOF Corporation] , Tert
-Butylperoxymaleic acid (Perbutyl MA manufactured by NOF Corporation), hydrogen peroxide and the like. Various organic peroxides can also be used. Such organic peroxides include, for example, tert-butylperoxy 2
-Ethyl hexanoate (Nippon Oil & Fats Co., Ltd. Perbutyl O), cumene hydroperoxide and the like.

In the production method of the present invention, a chain transfer agent can be used if necessary. Among them, dodecyl mercaptan and
Lauryl mercaptan, thioglycolic acid ester, thiomalic acid, mercaptoethanol, α-methylstyrene dimer and the like can be mentioned.

In the production method of the present invention, when redox polymerization is used as the emulsion polymerization method, a combination of various polymerization initiators as described above with a reducing agent can be used. Examples of such a reducing agent include sodium formaldehyde sulfoxylate [Superlite C manufactured by Mitsubishi Gas Chemical Co., Ltd.], sodium sulfite, sodium pyrosulfite, ascorbic acid, ferric chloride and the like.

As the electrolyte substance used in the production method of the present invention, any of various kinds of electrolyte substances can be used in addition to the above-mentioned polymerization initiator and reducing agent, and examples thereof include sodium chloride, potassium chloride and chloride. Metal halides and ammonium halides such as calcium, ammonium chloride, sodium bromide, potassium bromide and calcium bromide; anhydrous sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium carbonate, sodium hydrogen phosphate, potassium hydrogen phosphate; Metal salts and ammonium salts of various inorganic acids such as sodium hexametaphosphate, sodium hyposulfite, sodium nitrite, sodium tripolyphosphate, ammonium sulfate and the like.

As the electrolyte material, an inorganic electrolyte material, in particular, a water-soluble polymerization initiator, particularly a persulfate, can be suitably used, but the use of an organic electrolyte material does not impede the invention. Examples of such organic electrolyte substances include sodium formate, sodium acetate, zinc acetate, sodium tartrate, sodium benzoate, and the like, and organic carboxylate.

According to the production method of the present invention, a high nonvolatile content (for example, a nonvolatile content is 65% by weight or more, preferably 67% by weight or more).
~ 70% by weight), low viscosity (for example, 1500 mPa · s)
In order to easily obtain a resin emulsion having good pigment dispersibility, preferably at 200 to 1000 mPa · s), the average particle diameter is 20 by volume average as measured by a dynamic light scattering method.
It is preferably from 0 nm to 1 μm, especially 300
It is particularly preferable that the particle diameter is in the range of from nm to 600 nm and the particle size distribution is wide. As the particle size distribution, the ratio of the volume average particle size to the number average particle size is preferably 2.0 or more, more preferably 3.0 or more, and further has a bimodal particle size distribution. Particularly preferred is a resin emulsion. The molecular weight of the resin emulsion was measured by GPC and found to have a number average molecular weight of 20,000 to 1
It is preferable to be 100,000 and 100,000 to 1,000,000 in weight average molecular weight.

The coating composition of the present invention is characterized by containing the resin emulsion obtained by the production method of the present invention as an essential component, and blending various additives necessary for designing a water-based coating as needed. A coating composition comprising: The coating composition of the present invention may be of a room temperature drying type or a forced drying type, but is particularly suitable for a room temperature drying type.

Various additives can be used as the above-mentioned additives, for example, pigments, extenders, water, dispersants, wetting agents, defoamers, film-forming auxiliaries, antifreezing agents, pH adjusters, Examples include a flow regulator, an anti-cissing agent, a plasticizer, a thickener, an antiseptic, a fungicide, and an anti-skinning agent. Further, depending on the use, a modifying agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antioxidant, a rust inhibitor, etc. may be used alone or as necessary.
More than one species can be added. The coating composition of the present invention can be put to practical use as a coating, with or without such additives.

As the pigment or extender used herein, various pigments are listed. For example, as the organic pigment, various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc .;
Soluble azo pigments such as Carmine 6B and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorinated dyeing lakes such as rhodamine lake and methyl violet lake; quinoline lake; Various mordant dye pigments such as Fast Sky Blue; various vat dye pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments; various quinacridone pigments such as synchasia red B Pigments; various oxazine pigments such as oxazine violet; various condensed azo pigments such as chromophtal; aniline black;

Next, as the inorganic pigment, various chromates such as graphite, zinc chromate, molybdate orange and the like; various ferrocyan compounds such as navy blue and the like;
Various metal oxides such as titanium oxide, zinc oxide, mapico yellow, iron oxide, red iron oxide, chrome green, etc .; various sulfides or selenides such as cadmium yellow, cadmium red, mercury sulfide, etc .; barium sulfate, sulfuric acid Various sulfates such as lead; various silicate salts such as calcium silicate and ultramarine blue; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple. Various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, brass powder, etc .; flake pigments of these metals, mica flake pigments; mica flake pigments coated with metal oxides; Such as mica-like iron oxide pigments,
Metallic pigments and pearl pigments; graphite, carbon black and the like.

As extenders, precipitated barium sulfate,
Flour, precipitated calcium carbonate, calcium bicarbonate, dolomite, alumina white, silica, hydrated fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, Clay, kaolin, ocher and the like can be used.

Further, a plastic pigment [for example, Grandol PP- manufactured by Dainippon Ink and Chemicals, Inc.]
1000, PP-2000S) and the like.

A dispersant which can be added to the coating composition of the present invention;
Examples of the wetting agent include various types. Representative examples thereof include condensed phosphates such as sodium tripolyphosphate and sodium pyrophosphate; higher alcohols such as surfactant-type low-medium polymer dispersants, sodium oleate,
Anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl maleate sulfonates, and phosphates; nonionic surfactants such as polyethylene glycol derivatives, polyethers, and polyesters; polymer surfactants Agents, for example, polymeric polycarboxylates, polymeric polyesters,
Long chain polyamide salt of carboxylic acid, long chain polyamide phosphate, sodium lignin sulfonate, styrene-maleic acid copolymer salt, naphthalene sulfonic acid, polymer condensate salt of formalin; diisobutylene-maleic acid copolymer (Here, the term “salt” is a generic term for amine salts, ammonium salts, and neutralized salts of metals such as sodium and potassium.)

There are various types of thickeners or flow regulators that can be added to the coating composition of the present invention, for example, inorganic filler-based thickeners such as montmorillonite clay minerals and colloidal alumina; Methyl cellulose (M
C), cellulose-based thickeners such as carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylcellulose, hydrophobic group-modified hydroxycellulose, etc .; polyethylene glycol ether [Bissurf S manufactured by Kao Corporation]; Surfactant-based thickeners such as nonionic surfactant [DK Thickener SCT manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; BN Leveler H904 manufactured by San Nopco Co.]; Viscous rheology modifier;
Emulsion type, colloidal dispersion type primal ASE thickener (manufactured by Rohm &Haas); nonionic hydrophobic group-modified polyoxyethylene / urethane block copolymer (HEUR), hydrophobic group-modified alkali-soluble emulsion (HASE), etc. Polysaccharides (alginate, guar gum, mannan); polyacrylic acid,
Polyvinyl alcohol, polyvinylpyrrolidone and the like can be mentioned.

Further, as a flow regulator, a high boiling point solvent, a surfactant, siloxane and the like can be used.

The coating composition of the present invention may further contain, if necessary, a urethane resin, an epoxy resin, a polyester resin; a cellulose derivative such as nitrocellulose, cellulose acetate, cellulose acetate butyrate; Vinyl, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, polybutadiene, acrylonitrile -Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated rubber, cyclized rubber, petroleum resin, polyvinyl butyral, polyvinyl alcohol, polyethylene, polypropylene; chlorinated polyethylene, chlorinated polypropylene, etc. , Various halogenated polyolefins; polyvinylidene fluoride, amino resin; various curing agents such as polyisocyanate, block polyisocyanate, etc .; it can.

As the film-forming aid which can be added to the coating composition of the present invention, various ones can be used. Some examples thereof include cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve. Carbitols such as ethyl carbitol and butyl carbitol; cellosolve acetate; carbitol acetates; glycols such as ethylene glycol and diethylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate; -Trimethylpentanediol-1,
Examples thereof include alcohols such as 3-monoisobutyrate (Texanol manufactured by Eastman Chemical Company) and 2-ethylhexanol, solfit, dibutyl phthalate, and the like.

As the antifreezing agent, for example, methanol, ethylene glycol, diethylene glycol, propylene glycol, distilled glycerin and the like can be used.

Various preservatives and fungicides can be used. Examples of preservatives include 5-chloro-2-methyl-4-isothiazolin-3-one (CIT),
Methyl-4-isothiazolin-3-one (MIT),
1,2-benzisothiazolone-3-one (BIT);
Mornon 510, 950 manufactured by Katayama Chemical Industry Laboratory Co., Ltd.
610; Best side manufactured by Dainippon Ink and Chemicals, Inc.
700, FX; Activide CB, MV4 manufactured by So Chemicals Japan K.K .; 2-bromo-2-nitro-
1,3-propanediol preservative, hexahydro-
1,3,5-tris- (2-hydroxyethyl-S-triazine preservative; formalin; silver preservative as inorganic preservative (JMAC L manufactured by Dainippon Ink and Chemicals, Inc.)
P), copper-based preservatives and the like.
(4-thiazolyl) -benzimidazole (TBZ),
2- (methoxy-carbonyl-amino-benzimidazole (BCM), 2- (4-thiocyanomethylthio) benzothiazole (TCMTB), 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,
4,5,6-tetrachloroisophthalonitrile (TP
N) and the like. These can be used alone or 2 respectively.
More than one kind can be mixed and used.

Various ultraviolet absorbers, light stabilizers or antioxidants can be used, such as 2,4-dihydroxybenzophenone ("Seesorb 100"),
2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone ("Seesorb 101"), 2,2'-dihydroxy-
4,4'-methoxybenzophenone, 2-hydroxy-
Benzophenone ultraviolet absorbers such as 4-methoxy-5-sulfobenzophenone; 2- (3,5-ditert)
-Amyl-2-hydroxyphenyl) benzotriazole ("Tinuvin 328"), 2- (5-methyl-2-hydroxyphenyl) benzotriazole ("Tinuvin P"), 2- [2-hydroxy-3,5-di (1,1-
Various benzotriazole UV absorbers such as dimethylbenzyl) phenyl] -2-benzotriazole ("Tinuvin 900"); various salicylate UV absorbers such as phenyl salicylate ("Seesorb 201"); ethyl-2- Various substituted acrylonitrile UV absorbers, such as cyano-3,3'-diphenylacrylate ("Seesorb 501"); 2-ethoxy-2 '
Various oxalic anilide ultraviolet absorbers, such as ethyl oxac acid bisanilide ("Tinuvin 312");[2,2'-thiobis (4-tert-octylphenolate)]-2-ethylhexylamine-nickel (II) Various nickel complex UV absorbers such as (Seesorb 612NH); examples of liquid UV absorbers include Tinuvin 384, Tinuvin 1130, Tinuvin 400 (manufactured by Ciba Specialty Chemicals), and the like. Further, as a water-dispersion type ultraviolet absorber, Orisorb 7090E [manufactured by Orion Kasei Co., Ltd.], San
duvor3041Disp. , PT-21Dis
p. , 3225 Disp. JPV Disp. (Manufactured by Clariant Japan Co., Ltd.) and Luck Star DX-104 (manufactured by Dainippon Ink and Chemicals, Inc.).

As the light stabilizer, for example, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate (“Tinuvin 292”), bis (2,2,6,6)
-Tetramethyl-4-piperidyl) sebacate ("Tinuvin 770"), bis (1,2,2,2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate Hindered amine light stabilizers such as 6-pentamethyl-4-piperidyl) (“Tinuvin 144”);
ndvor 3051 Disp. JP31 Disp.
[Clariant Japan Co., Ltd.] and the like.

Examples of the antioxidant include 3,5-di-tert-4-hydroxytoluene (“BHT Swannox”) and tetrakis- [methylene- (3,5-di-tert-butyl-4-hydroxyhydro). Cinnamate)] (“Irganox 1010”) and the like.

As the defoaming agent, various aqueous defoaming agents can be used. For example, lower alcohols such as methanol, ethanol and butanol; higher alcohols such as amyl alcohol, polypropylene glycol and derivatives thereof; oleic acid, tall oil Fats and oils such as mineral oils and soaps; surfactants such as sorbitan fatty acid esters, polyethylene glycol fatty acid esters, and pluronic nonionic surfactants; and silicon-based surfactants such as siloxane and silicone resins. , Used in combination.

Typical antifoaming agents include B-series (made by Asahi Denka Kogyo KK) such as Adecanate B and Adecanate B1068; and SN deformers such as Formaster DL, Nopco NXZ, SN Deformers 113, 325, 308 and 368. Series; Dehydran 1293, Dehydran 1513 [manufactured by San Nopco Co., Ltd.]; Furonon SB-11
0N, SB-210, 510, 551, AQUALEN 80
0,805, AQUALEN 1488 [Kyoeisha Chemical Co., Ltd.
Surfynol 104E (Acetylene-based antifoaming agent manufactured by Air Products &Chemicals); KS-607A (Shin-Etsu Chemical Co., Ltd.); FS Antifoam (Dow Corning); BYK-020, 031, 073 , W (manufactured by Big Chemie); Dehydran 981 (manufactured by Henkel Hakusui); Epan-410, 710, 720 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Tego Foamex series (TEGO
Goldschmidt); Foam Rex-74
7, TY-10, EP series (manufactured by Nichika Chemical Co., Ltd.) and the like.

As the pH adjuster, various agents can be used. For example, ammonia, triethylamine, N, N-
Amines such as dimethylaminoethanol, 2-amino-2-methylpropanol (AMP), diethanolamine and triethanolamine; alkali metals such as sodium hydroxide and potassium hydroxide can be used.

In order to produce the coating composition of the present invention, for example, a method of mixing the above-mentioned various components, and then dispersing and stirring with various dispersing machines such as a colloid mill and a disper to form a coating composition. Has been adopted.

As the coating method according to the present invention, known and commonly used coating methods can be employed. Examples of such coating methods include spray coating, roller coating, tile gun coating, ricin gun coating, and brush coating. No. As described above, room temperature drying can be suitably used as described above.

Here, as typical examples of the substrate to be coated, various inorganic building materials such as cement, lightweight foam concrete, slate board, etc .; tiles; glass; aluminum, stainless steel steel,
Various metal materials or metal products such as chrome plating and the like can be mentioned.

[0080]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Reference Examples, which are only one embodiment of the present invention, and the present invention is by no means limited to these Examples. It is not limited by. In the following, all parts and percentages are by weight unless otherwise specified.

Example 1 (Preparation of pre-emulsion) An emulsifier having the following composition and ion-exchanged water were charged into a beaker and sufficiently dissolved. A vinyl-based monomer was charged therein and stirred and emulsified to prepare a pre-emulsion. Deionized water 160.0 parts Perex SSH * 1) 16.0 parts Neugen EA-150 * 2) 16.0 parts n-butyl acrylate 360.0 parts Styrene 40.0 parts Methyl methacrylate 390.0 parts 80% methacryl Aqueous acid solution 10.0 parts

* 1): Anionic surfactant (disodium alkyldiphenyl ether disulfonate) manufactured by Kao Corporation * 2): Nonionic surfactant (polyoxyethylene nonylphenyl ether) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

(Preparation of Polymerization Initiator Solution for Dropping) 3.2 parts of ammonium persulfate and 28 parts of ion-exchanged water were placed in a beaker and sufficiently stirred and dissolved at room temperature to prepare a polymerization initiator solution for dropping.

[Synthesis of Resin Emulsion] In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet,
128 parts of ion-exchanged water and 2.4 parts of ammonium persulfate were added, and the temperature was raised to 80 ° C. over 30 minutes under a nitrogen seal. Next, the pre-emulsion and the polymerization initiator solution for dropping were added dropwise over 4 hours, and thereafter maintained for 60 minutes, thereby effecting emulsion polymerization while lowering the concentration of the electrolyte substance in the system, and then cooling. Using ammonia water and ion-exchanged water, the pH is 7.3 and the nonvolatile content is 6
The viscosity was measured to be 390 mPa · s by a BM-type rotational viscometer at 8.1% and a measurement temperature of 25 ° C. to obtain a resin emulsion. This is called (EM-1).

Table 1 (1) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, aggregation of the obtained resin emulsion (EM-1). Shows the solids content.

Example 2 (Preparation of pre-emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Ion-exchanged water 120.0 parts Newcol 271A * 3) 17.0 parts Emulgen 911 * 4) 16.0 parts n-butyl acrylate 370.0 parts styrene 80.0 parts methyl methacrylate 350.0 parts 80% acrylic acid aqueous solution 5 .0 copies

* 3): Anionic surfactant (Disodium dodecyl diphenyl ether disulfonate) manufactured by Nippon Emulsifier Co., Ltd. * 4): Nonionic surfactant (polyoxyethylene nonyl phenyl ether) manufactured by Kao Corporation

(Preparation of aqueous solution of polymerization initiator for dropping) 3.5 parts of sodium persulfate was dissolved in 25.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Resin Emulsion) In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet,
120 parts of ion-exchanged water was charged, the temperature was raised to 80 ° C. while stirring under a nitrogen seal, and 3.6 parts of sodium persulfate was charged. After holding for 10 minutes, the pre-emulsion and the aqueous solution of the polymerization initiator for dropping are added dropwise for 4 hours, and by holding for further 60 minutes, emulsion polymerization is performed while lowering the concentration of the electrolyte substance in the system. Cool. Using ammonia water and ion-exchanged water, the pH was adjusted to 8.1, the nonvolatile content was adjusted to 69.5%, and the viscosity measured by a BM-type rotational viscometer was adjusted to 1050 mPa · s to obtain a resin emulsion. This is called (EM-2).

Table 1 (1) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, aggregation of the obtained resin emulsion (EM-2). Shows the solids content.

Example 3 (Preparation of pre-emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 100.0 parts Perex SSH * 1) 15.0 parts Latemul E-150 * 5) 25.0 parts 2-ethylhexyl acrylate 108.0 parts n-butyl acrylate 180.0 parts Styrene 120.0 parts Methyl methacrylate 288.0 parts 80% aqueous solution of acrylic acid 6.0 parts Dimethylaminoethyl methacrylate 0.6 part

* 5): An anionic facial surfactant (sodium polyoxyethylene lauryl ether sulfate) manufactured by Kao Corporation

(Preparation of aqueous solution of polymerization initiator for dropping) 4.8 parts of ammonium persulfate was dissolved in 30 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Resin Emulsion) In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet,
130 parts of ion-exchanged water, 1.0 part of sodium chloride and 0.2 parts of Perex SSH as an electrolyte were charged, and the temperature was raised to 80 ° C. under a nitrogen seal. In order to form initial particles at 80 ° C., 5 parts of the pre-emulsion
After 5 minutes, 1.0 part of ammonium persulfate was replaced with 2 parts of ion-exchanged water.
The polymerization initiator aqueous solution dissolved in 0 parts was charged into the reactor.
After the addition of ammonium persulfate, the mixture is held for 30 minutes, and then the remaining pre-emulsion and the aqueous solution of the polymerization initiator are added dropwise over 4 hours, and further maintained for 60 minutes to reduce the concentration of the electrolyte substance in the system. Emulsion polymerization was performed, and then the mixture was cooled. Using ammonia water and ion-exchanged water, the pH was adjusted to 7.9, the nonvolatile content was adjusted to 67.7%, and the viscosity measured by a BM-type rotational viscometer was adjusted to 1280 mPa · s to obtain a resin emulsion. This is (EM-
3).

Table 1 (1) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, and aggregation of the obtained resin emulsion (EM-3). Shows the solids content.

Example 4 (Preparation of pre-emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 140.0 parts Newcol 293 * 6) 15.0 parts Hytenol N-08 * 7) 2.0 parts Neugen EA-170S * 8) 17.0 parts n-butyl acrylate 320.0 parts n- Butyl methacrylate 50.0 parts Methyl methacrylate 420.0 parts 80% aqueous solution of acrylic acid 10.0 parts

* 6): Anionic surfactant (polyoxyethylene alkyl ether sulfosuccinate disodium) manufactured by Nippon Emulsifier Co., Ltd. * 7): Anionic surfactant (polyoxyethylene manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Alkylene phenyl ether sulfate ammonium) * 8): Nonionic surfactant (polyoxyethylene nonyl phenyl ether) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

(Synthesis of Resin Emulsion) In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet,
160 parts of ion-exchanged water was added, and the temperature was raised to 80 ° C. under a nitrogen seal. At 80 ° C., 3.6 parts of ammonium persulfate were batch-charged, and after 20 minutes, the pre-emulsion was dropped over 4 hours, and further maintained for 60 minutes to reduce the electrolyte substance concentration in the system. Emulsion polymerization was performed, and then the mixture was cooled. Using ammonia water and ion-exchanged water, pH 8.1, nonvolatile content 67.3%, BM
The viscosity was measured so as to be 780 mPa · s as measured by a mold viscometer to obtain a resin emulsion. This is (EM-
4).

Table 1 (2) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, aggregation of the obtained resin emulsion (EM-4). Shows the solids content.

Example 5 (Preparation of pre-emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 130.0 parts Perex SSH * 1) 16.0 parts Neugen EA-130T * 9) 20.0 parts n-butyl acrylate 350.0 parts Methyl methacrylate 380.0 parts Styrene 80.0 parts 80% acrylic acid Aqueous solution 10.0 parts

* 9): Nonionic surfactant (polyoxyethylene nonylphenyl ether) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

(Synthesis of emulsion) Thermometer, stirrer,
130 parts of ion-exchanged water was charged into a reaction vessel equipped with a reflux condenser and a nitrogen inlet, and heated to 60 ° C. under a nitrogen seal. At 60 ° C., 5 parts of the pre-emulsion are charged,
After dispersing for 10 minutes, 1.0 part of a 0.5% aqueous solution of ferric chloride was added, and 2.5 parts of ammonium persulfate was dissolved in 12 parts of ion-exchanged water. A solution prepared by dissolving 5 parts in 8 parts of ion-exchanged water was charged to form initial particles.

After 20 minutes, the remaining pre-emulsion is
A solution in which 2.7 parts of ammonium persulfate is dissolved in 28 parts of ion-exchanged water (aqueous polymerization initiator aqueous solution) and a solution in which 3.7 parts of sodium pyrosulfite is dissolved in 28 parts of ion-exchanged water (aqueous reducing agent solution) Over 4 hours,
After the redox polymerization, the emulsion was held for another 60 minutes to perform emulsion polymerization while lowering the concentration of the electrolyte substance in the system, and then cooled. Using ammonia water and ion-exchanged water, the pH is 8.0 and the nonvolatile content is 68.2.
%, And adjusted to have a viscosity of 760 mPa · s as measured by a BM-type viscometer to obtain a resin emulsion. This is designated as (EM-5).

Table 1 (2) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, and aggregation of the obtained resin emulsion (EM-5). Shows the solids content.

Example 6 (Preparation of pre-emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 130.0 parts Newcol 271NH * 10) 16.0 parts Emulgen 920 * 11) 16.0 parts 2-ethylhexyl acrylate 650.0 parts Methyl methacrylate 65.0 parts n-butyl methacrylate 65.0 parts 80% Methacrylic acid aqueous solution 10.0 parts

* 10): Anionic surfactant (manufactured by Nippon Emulsifier Co., Ltd.) (diamonium dodecyl diphenyl ether disulfonate) * 11): Nonionic surfactant (polyoxyethylene nonyl phenyl ether) manufactured by Kao Corporation

(Preparation of aqueous solution of polymerization initiator for dropping) 3.5 parts of potassium persulfate was dissolved in 25.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of emulsion) Thermometer, stirrer,
130 parts of ion-exchanged water was charged into a reaction vessel equipped with a reflux condenser and a nitrogen inlet, and the temperature was raised to 80 ° C. under a nitrogen seal. At 80 ° C., charge 5 parts of the pre-emulsion,
After dispersing for 10 minutes, a solution prepared by dissolving 2.4 parts of potassium persulfate in 16 parts of ion-exchanged water and a solution prepared by dissolving 2.4 parts of sodium bicarbonate in 16 parts of ion-exchanged water were added and the initial solution was added. Particles were formed.

After 20 minutes, the remaining pre-emulsion and the aqueous solution of the polymerization initiator for dropping are added dropwise for 4 hours, and the mixture is held for 60 minutes to carry out emulsion polymerization while lowering the concentration of the electrolyte substance in the system. Then it was cooled. Using ammonia water and ion-exchanged water, the pH is 7.
5. The resin emulsion was obtained by adjusting the nonvolatile content to 68.4% and the viscosity measured by a BM type rotational viscometer to be 560 mPa · s. This is called (EM-6).

Table 1 (2) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, final emulsifier concentration, and aggregation of the obtained resin emulsion (EM-6). Shows the solids content.

Comparative Example 1 (Preparation of Pre-Emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Ion-exchanged water 160.0 parts Perex SSH * 1) 16.0 parts Neugen EA-150 * 2) 16.0 parts n-butyl acrylate 360.0 parts Styrene 40.0 parts Methyl methacrylate 390.0 parts 80% acrylic acid Aqueous solution 10.0 parts

(Preparation of aqueous solution of polymerization initiator for dropping) 4.3 parts of ammonium persulfate was dissolved in 50.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Comparative Resin Emulsion) A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet was charged with 150 parts of ion-exchanged water.
2 parts of SH and 0.60 parts of ammonium persulfate were charged, and the temperature was raised to 80 ° C. over 30 minutes under a nitrogen seal. Next, the pre-emulsion and the aqueous solution of the polymerization initiator for dropping were added dropwise for 4 hours, and the mixture was held for 60 minutes to carry out emulsion polymerization without decreasing the concentration of the electrolyte substance in the system, and then cooled. Using ammonia water and ion-exchanged water, the pH was 8.0, the nonvolatile content was 61.6%, and the viscosity measured by a B-type viscometer at a measurement temperature of 25 ° C. was 4300.
The pressure was adjusted to mPa · s to obtain a comparative resin emulsion. This is called (EM-1 ').

Table 1 (3) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, and final emulsifier of the obtained comparative resin emulsion (EM-1 '). The concentration and the amount of aggregated solid are shown.

Comparative Example 2 (Preparation of Pre-Emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 120.0 parts Newcol 271A * 3) 17.0 parts Emulgen 911 * 4) 16.0 parts n-butyl acrylate 370.0 parts Styrene 80.0 parts Methyl methacrylate 350.0 parts 80% acrylic acid aqueous solution 5.0 parts

(Preparation of aqueous solution of polymerization initiator for dropping) 3.0 parts of sodium persulfate was dissolved in 40.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Comparative Resin Emulsion) 400 parts of ion-exchanged water was charged into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, and Hytenol N-08 was used as a surfactant. Four parts were charged, completely dissolved, and heated to 80 ° C. under a nitrogen seal. Next, 30 parts of the pre-emulsion was charged and held for 10 minutes, and then a solution prepared by dissolving 0.4 part of sodium persulfate in 10 parts of ion-exchanged water was charged to form initial particles.
After 15 minutes, the pre-emulsion and the aqueous solution of the polymerization initiator for dropping were added dropwise for 4 hours, and the mixture was held for 60 minutes to carry out emulsion polymerization while increasing the concentration of the electrolyte substance in the system, followed by cooling. Using ammonia water and ion-exchanged water, the pH is 8.2 and the nonvolatile content is 50.2.
%, And adjusted so that the viscosity measured by a B-type viscometer was 860 mPa · s to obtain a comparative resin emulsion. This is called (EM-2 ').

Table 1 (3) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, and final emulsifier of the obtained comparative resin emulsion (EM-2 '). The concentration and the amount of aggregated solid are shown.

Comparative Example 3 (Preparation of Pre-Emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 150.0 parts Newcol 271NH * 10) 16.0 parts Emulgen 920 * 11) 16.0 parts 2-ethylhexyl acrylate 650.0 parts Methyl methacrylate 65.0 parts n-butyl methacrylate 65.0 parts 80 % Acrylic acid aqueous solution 10.0 parts

(Preparation of aqueous solution of polymerization initiator for dropping) 5.0 parts of sodium persulfate was dissolved in 50.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Comparative Resin Emulsion) A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet was charged with 240 parts of ion-exchanged water and Hytenol N-0.
8 Charge 2.4 parts, raise the temperature to 80 ° C. under a nitrogen seal, then add 20 parts of the pre-emulsion, hold for 10 minutes, and then add 0.5 parts of sodium pyrosulfite and 0.5 parts of ammonium persulfate. It was charged to form initial particles. Twenty minutes later, the remaining pre-emulsion and the aqueous solution of the polymerization initiator for dropping were carried out for 4 hours, and the mixture was held for 60 minutes to carry out emulsion polymerization while slightly increasing the concentration of the electrolyte substance in the system, and then cooled. Using ammonia water and ion-exchanged water, the pH was 8.3, the nonvolatile content was 58.0%, and the viscosity was 3700 measured by a B-type viscometer.
The pressure was adjusted to mPa · s to obtain a comparative resin emulsion. This is called (EM-3 ').

Table 1 (3) shows the volume average particle size, particle size distribution, initial electrolyte concentration, final electrolyte concentration, initial emulsifier concentration, and final emulsifier of the obtained comparative resin emulsion (EM-3 '). The concentration and the amount of aggregated solid are shown.

Comparative Example 4 (Preparation of Pre-Emulsion) A pre-emulsion was prepared in the same manner as in Example 1 with the following composition. Deionized water 140.0 parts Newcol 293 * 6) 15.0 parts Hytenol N-08 * 7) 2.0 parts Neugen EA-170 * 12) 17.0 parts n-butyl acrylate 320.0 parts n- Butyl methacrylate 50.0 parts Methyl methacrylate 420.0 parts 80% aqueous solution of acrylic acid 10.0 parts

* 12): Nonionic surfactant (polyoxyethylene nonylphenyl ether) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

(Preparation of aqueous solution of polymerization initiator for dropping) 5.4 parts of ammonium persulfate was dissolved in 50.0 parts of ion-exchanged water to prepare an aqueous solution of a polymerization initiator for dropping.

(Synthesis of Comparative Resin Emulsion) A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet was charged with 130 parts of ion-exchanged water, and heated to 80 ° C. under a nitrogen seal. At 80 ° C., 5 parts of the pre-emulsion were charged, and 15 minutes later, 0.7 parts of sodium persulfate was charged to form initial particles. After 30 minutes, the dropping of the remaining pre-emulsion and the aqueous solution of the polymerization initiator for dropping was started, and by dropping over 4 hours, emulsion polymerization was to be performed without lowering the concentration of the electrolyte substance in the system. Immediately before the completion of the dropwise addition, the viscosity rapidly increased and stirring became difficult, so the reaction was interrupted.

Table 1 (4) shows the initial electrolyte concentration, the end electrolyte concentration, the initial emulsifier concentration, and the end emulsifier concentration for those in which the reaction was interrupted.

[0128]

[Table 1]

(Footnotes to Table 1) Volume average particle size: Measured by dynamic light scattering using MICROTRAC UPA manufactured by Nikkiso Co., Ltd. -Particle size distribution: expressed as the ratio (mv / mn) between the volume average particle size (mv) and number average particle size (mn) measured by dynamic light scattering method using MICROTRAC UPA manufactured by Nikkiso Co., Ltd.・ Initial electrolyte concentration: The concentration of the electrolyte substance in the reaction vessel before the start of pre-emulsion dripping (not including surfactant).・ End electrolyte concentration: The concentration of the electrolyte substance in the reaction vessel at the end of the pre-emulsion dropping (not including the surfactant).・ Initial emulsifier concentration: The concentration of the emulsifier in the reaction vessel before the start of pre-emulsion dripping (excluding electrolyte substances).・ Emulsifier concentration at the end: The concentration of the emulsifier in the reaction vessel at the end of the pre-emulsion dropping (excluding the electrolyte substance). -Aggregated solids: The wet weight after filtration with a 100-mesh filter cloth is expressed in grams per 1 kg of resin emulsion.

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

The coating compositions for the main component of the single-layer elastic coating were prepared using the emulsions (EM-1) to (EM-5) prepared in Examples 1 to 5. In Examples 7 to 11, the blending was performed by a mill base method, which is a known coating composition, and in Examples 12 to 17, a dry blending method capable of designing a paint having a higher non-volatile content and a lower viscosity was performed. For comparison, comparative resin emulsions (EM-1 ′) to (EM-
Using 3 '), a coating composition for the main material of the single-layer elastic coating was similarly compounded.

Examples 7 to 11 Raw materials having the following composition were passed through a colloid mill twice to be stirred and dispersed to prepare a mill base.

Titanics JR-600A * 13) 68.1 parts Luminous * 14) 101.8 parts Poise 530 * 15) 0.8 parts Poise 521 * 16) 0.8 parts 10% NaTPP * 17) 3.3 Part Adecanoate B-190 * 18) 0.5 part Ethylene glycol 7.1 parts Ion exchange water 71.0 parts 28% ammonia water 1.4 parts Subtotal 254.8 parts

* 13): Titanium oxide manufactured by Teica Co., Ltd. * 14): Fine-particle calcium carbonate manufactured by Maruo Calcium Co., Ltd. * 15): Pigment dispersant manufactured by Kao Corporation * 16): Pigment dispersion manufactured by Kao Corporation * 17): Sodium tripolyphosphate (pigment dispersant) * 18): Defoaming agent manufactured by Asahi Denka Kogyo Co., Ltd.

The obtained mill base was placed in a disper,
While stirring, the following raw materials were added sequentially, and after the addition was completed, 1
The mixture was stirred at 000 rpm for 20 minutes to prepare a coating composition as a main material of a single-layer elastic coating. Properties of the obtained coating composition are shown in Tables 2 (1) and (2), respectively.

The resin emulsion (EM-1)
The coating compositions obtained using (EM-5) are respectively referred to as (Paint 1-1) to (Paint 1-5). Further, the obtained (paint 1-1) had a nonvolatile content of 61%, a PWC (pigment weight concentration) of 27%, and a PVC (pigment volume concentration) of 11%.
The other paints were almost the same.

Any of (EM-1) to (EM-5) 652.0 parts Texanol * 19) 45.6 parts 5% Hymetrose 90 SH-4000 * 20) 35.0 parts 15% Adecanol UH-420 * 21) 11.3 parts Adekaneto B-190 * 18) 1.3 parts total 1000.0 parts

* 19): Eastman Chemical
* 20): A thickener manufactured by Shin-Etsu Chemical Co., Ltd. * 21): A thickener manufactured by Asahi Denka Kogyo Co., Ltd.

Comparative Examples 5 to 6 Mill bases were prepared in the same manner as in Examples 7 to 11. The obtained mill base was put into a disper, and the following raw materials were sequentially added with stirring, and after the addition was completed, the mixture was stirred at 1000 rpm for 20 minutes to prepare a coating composition for a main material of a single-layer elastic coating. The properties of the obtained coating composition are shown in Table 2 (3).

The coating composition obtained by using the resin emulsion (EM-1 ') or (EM-2') was
(Paint 1-1 ') or (Paint 1-2'). The nonvolatile content of the obtained (Paint 1-1 ') was 57%,
WC (pigment weight concentration) was 27%, PVC (pigment volume concentration) was 11%, and the other paints were almost the same.

[0143]

[Table 5]

(Note 1) Paint viscosity: Measured with a BH type viscometer at a measurement temperature of 20 ° C. (Note 2) Thixotropic coefficient: calculated by the following equation. Thixotropic coefficient = [(logB−logA) / (logrA−logr)
B)] where A and B are the viscosities at rotational speeds rA and rB (mP
a ・ s)

[0145]

[Table 6]

[0146]

[Table 7]

Examples 12 to 16 The following materials were sequentially added to a disperser with stirring.
After completion of the addition, the mixture was stirred and dispersed at 2000 rpm for 20 minutes to prepare a coating composition for a main material of a single-layer elastic coating. The properties of the obtained coating compositions are shown in Table 3 (1).
To (2).

The resin emulsion (EM-1)
The paint compositions obtained using (EM-5) are referred to as (paint 2-1) to (paint 2-5), respectively. The nonvolatile content of the obtained (paint 2-1) was 67%, and the PWC was 26%.
% And PVC were 10%, and the other paints were almost the same.

Any of (EM-1) to (EM-5) 728.5 parts Primal 731 * 22) 5.9 parts Propylene glycol 17.7 parts Chisso Sizer CS-12 * 23) 43.0 parts 28% ammonia water 1.9 parts 3% Cellosize QP4400H * 24) 23.3 parts Chitanikkusu JR-600A * 13) 106.8 parts PGW * 25) 71.4 parts SN Defoamer 380 * 26) 1.5 parts total 1000 .0 copies

* 22): Pigment dispersant manufactured by Rohm & Haas * 23): Film aid manufactured by Chisso Co., Ltd. * 24): Thickener manufactured by UCC * 25): Calcium carbonate manufactured by Shiroishi Kogyo * 26) : Defoamer manufactured by Sun Nopco

Example 17 The following raw materials including the emulsion (EM-6) prepared in Example 6 were sequentially added to a disper.
After stirring and dispersing at 0 rpm for 40 minutes, a coating composition for the main component of the multilayer elastic coating [non-volatile content 80%, PWC
(Pigment weight concentration) 69%, PVC (pigment volume concentration) 47
%] Was prepared. The properties of the obtained coating composition are shown in Table 3 (2). Moreover, the obtained coating composition is called (paint 2-6).

(EM-6) 356.8 parts Ion-exchanged water 46.7 parts Adecanol B-187 * 27) 12.2 parts Demol EP * 28) 4.7 parts Ethylene glycol 7.5 parts Taipaque R-780 * 29) 28.0 parts calcium carbonate NS-100 * 30) 532.4 parts of 15% Adekanol UH-420 * 31) 1.4 parts of 3% Cellosize QP-4400H * 24) 10.3 parts total 1000.0 parts

* 27): Pigment dispersant manufactured by Asahi Denka Kogyo Co., Ltd. * 28): Pigment dispersant manufactured by Kao Corporation * 29): Titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 30): Nitto Powder Co., Ltd. ) Filler * 31): Thickener manufactured by Asahi Denka Kogyo Co., Ltd.

Comparative Examples 7 and 8 The following materials were sequentially added to a disper while stirring,
After completion of the addition, the mixture was stirred and dispersed at 2000 rpm for 20 minutes to prepare a coating composition for a main material of a single-layer elastic coating. Table 3 (3) shows the properties of the obtained coating compositions.
Shown in

The coating composition obtained by using the resin emulsion (EM-1 ') or (EM-2') was
(Paint 2-1 ') or (Paint 2-2'). The nonvolatile content of the obtained (paint 2-1 ′) was 63%,
WC was 27%, PVC was 11%, and the other paints were almost the same.

(EM-1 ') or (EM-2') 724.3 parts Poise 521 * 16) 6.3 parts Ethylene glycol 18.0 parts Texanol * 19) 43.6 parts 28% aqueous ammonia 1.8 part 5% Haimetorozu 90 SH4000 * 20) 23.7 parts Chitanikkusu JR-600A * 13) 72.5 parts Luminous * 14) 108.4 parts Adekaneto B-190 * 18) 1.4 parts total 1000.0 parts

Comparative Example 9 The following raw materials including the emulsion (EM-3 ') prepared in Comparative Example 3 were sequentially added to a disper, and after completion of the addition, the mixture was stirred and dispersed at 3000 rpm for 40 minutes to obtain a main material of the multilayer elastic paint. A coating composition (non-volatile content: 79%, PWC (pigment weight concentration): 69%) was prepared. Table 3 (3) shows the properties of the obtained coating composition.
Shown in Further, the obtained coating composition was coated with (paint 2-3 ').
Called.

EM-3 '117.0 parts 10% NaTPP * 17) 1.5 parts Demol EP * 28) 1.5 parts Ethylene glycol 3.0 parts SN deformer 154 * 32) 1.5 parts Neugen EA -120 * 33) 1.5 parts Cell top HP-103 * 34) 1.5 parts Charcoal NS-100 * 30) 72.0 parts Charcoal SS-30 * 35) 64.0 parts Cold water # 70 * 36 ) 6.0 parts Tipaque R-550 * 37) 2.0 parts Haimetorozu 90 SH-15000 * 38) 0.3 parts (28%) aqueous ammonia 1.0 parts total 272.8 parts

* 32): Defoaming agent manufactured by Sun Nopco * 33): Nonionic surfactant (polyoxyethylene nonylphenyl ether) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. * 34): Filling manufactured by Kojin Co., Ltd. * 35): Filling material manufactured by Nitto Powder Chemical Co., Ltd. * 36): Filling material manufactured by Nitto Powder Chemical Co., Ltd. * 37): Titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 38): Increased by Shin-Etsu Chemical Co., Ltd. Adhesive

[0160]

[Table 8]

[0161]

[Table 9]

[0162]

[Table 10]

Reference Example 1 (Formulation for finish coating of multilayer elastic paint) A raw material having the following composition was passed through a colloid mill twice to be stirred and dispersed to prepare a mill base.

Titanics JR-600A * 13) 265.3 parts orotane SG-1 * 39) 7.0 parts 10% NaTPP * 17) 5.2 parts Neugen EA-120 * 33) 2.3 parts Ethylene glycol 19 .2 parts Best side FX * 34) 1.1 parts SN deformer 121 * 40) 0.9 parts Ion-exchanged water 77.6 parts 28% ammonia water 0.5 parts Subtotal 379.1 parts

* 39): Pigment dispersant manufactured by Rohm & Haas * 40): Defoamer manufactured by Sun Nopco

The obtained mill base was placed in a disper,
While stirring, the following raw materials were added sequentially, and after the addition was completed, 1
The mixture was stirred at 2,000 rpm for 20 minutes to obtain a coating composition for the finish coating of a multilayer elastic paint [nonvolatile content 55%, PWC
(Pigment weight concentration) 47%, PVC (Pigment volume concentration) 18
%] Was prepared. Table 4 shows the properties of the obtained coating composition. In addition, the obtained coating composition is called (paint 4).

[0167] Boncoat CG-5030 * 41) 582.2 parts of Texanol * 19) 27.7 parts of 3% Cellosize QP-4400H * 24) 9.7 parts Primal RM-8 * 42) 1.3 parts Total 1000. 0 copies

* 41): Acrylic-urethane composite emulsion manufactured by Dainippon Ink and Chemicals, Inc. * 42): Pigment dispersant manufactured by Rohm & Haas

[0169]

[Table 11]

(Footnote to Table 4) Coating viscosity: Measured at a temperature of 20 ° C. with a Stormer viscometer.

As can be seen from Tables 2 and 3, the coating composition using the resin emulsion according to the present invention can be used in both the mill base method (Examples 7 to 11) and the dry blend method (Examples 12 to 17). Indicates that the resin composition has a higher solid content and a lower viscosity than the coating composition using the comparative resin emulsion.

Examples 18 to 28 and Comparative Examples 10 to 14 (Dryability test) (Paints 1-1) to (Paints 1 to 5) prepared in Examples 7 to 11 (Examples of paint composition of a mill base method)
Examples 12 to 17 (Examples of dry blend paint formulation)
(Paint 2-1) to (Paint 2-6), Comparative Example 5
(Paint 1-1 ') to (Paint 1-2'), Comparative Examples 7 to 9 (comparative examples of mill-based paint).
(Paint 2-1 ′) to (Paint 2-3 ′) (all white paint compositions) prepared in (Comparative paint blending example of dry blend system) were applied to a glass plate at room temperature with an applicator. Then, the white paint was transferred to black ketone paper by putting black Kent paper at intervals of 5 minutes, and the drying property was evaluated by the time until the white paint was not transferred. These results are shown in Tables 5 (1) to (3) and Table 6 (1) to
It is shown in (3).

(Measurement of Gloss Value) Each of the coating compositions prepared in Examples 7 to 16 and Comparative Examples 5 to 8 was applied to a glass plate at a thickness of 0.076 mm using an applicator.
After drying at 20 ° C. and a relative humidity of 65% for one week, a 60 ° specular gloss value was measured with a specular gloss meter. The results are shown in Tables (1) to (3) and Tables (1) to (3).

Each of the coating compositions prepared in Example 17 and Comparative Example 9 was applied to a glass plate to a thickness of 0.152 mm with a winding bar, and dried at 20 ° C. and 65% relative humidity for 24 hours. After that, paint 4 was coated thereon with an applicator to a thickness of 0.076 mm, and
After drying at 0 ° C. and a relative humidity of 65% for one week, a 60 ° specular gloss value was measured. The results are shown in Tables 6 (2) and (3).

(Application Example of Single-Layer Elastic Coating) Acrydick A-181 [Normal dry solvent-based acrylic resin manufactured by Dainippon Ink and Chemicals, Ltd.]
A 15% diluted solution of
It was coated at 0 g / m ² and dried for 1 hour at 20 ° C. and 65% relative humidity.

Next, Examples 7 to 16 and Comparative Examples 5 to
Each of the coating compositions prepared in No. 8 was 25000 m
Diluted with water to Pa · s and applied 600g with sand roller
/ M ^Two 2 hours at 20 ° C and 65% relative humidity
After drying for a while, Examples 7-16 and ratio
Each of the coating compositions prepared in Comparative Examples 5 to 8 was used for 25
000mPa · s, and apply with sand roller
0 g / m^Two At 20 ° C, relative
Dry at 65% humidity for 1 week to obtain a painted board with uneven pattern
Was. Using this painted plate, a general coating film physical property test (water resistance test)
Test, alkali resistance test and pattern thinning test).
The results are shown in Tables 5 (1)-(3) and 6 (1)-
It is shown in (3).

(Application Example of Multi-layer Elastic Coating) Acrylic A-181 [Normal dry solvent-based acrylic resin manufactured by Dainippon Ink and Chemicals, Ltd.]
A 15% diluted solution of
It was coated at 0 g / m ² and dried for 1 hour at 20 ° C. and 65% relative humidity.

Then, each of the coating compositions prepared in Example 17 and Comparative Example 9 was spray-coated with a lysing gun at a coating amount of 1.5 kg / m ² , and was subjected to 20 ° C. and a relative humidity of 6%.
After drying at 5% for 5 hours, each of the coating compositions similarly prepared in Example 17 and Comparative Example 9 was spray-coated with a tile gun at an application amount of 1.2 kg / m ² , respectively. , 20 ° C and 65% relative humidity for 24 hours.

Further, as a finish coating material, the coating material 4 prepared in Reference Example 1 was applied with a medium hair roller at an application amount of 700 g / m 2.
² and dried for 1 week at 20 ° C. and a relative humidity of 65% to obtain a coated plate. Using the coated plate, a general coating film physical property test (a water resistance test, an alkali resistance test, and a pattern thinning test) was performed. The results are shown in Table 6 (2)
It is shown in (3).

General coating film physical property test (1) Water resistance test: The coated plate was immersed in water at room temperature for 10 days and evaluated according to the following four grades. A: No change at all. Good: Some whitening and / or blistering are observed. Acceptable: Whitening and / or blistering are recognized, but those judged to be practically usable. Impossible: Whitening and / or blisters are remarkable and judged to be unusable for practical use. (2) Alkali resistance test: 2% NaO at room temperature
It was immersed in an H aqueous solution for 10 days and evaluated on the following four levels. A: No change at all. Good: A slight change and / or blister is recognized. OK: Changes and / or blisters are recognized, but those judged to be practically usable. Impossible: Changes and / or blisters are remarkable and judged to be unusable for practical use. (3) Pattern thinning test: The height of the concavo-convex pattern of the coating film was visually judged in the following four stages. Excellent ... Thin with little thinness and sharpness of unevenness stands out. Good: Some thinness is recognized, but unevenness is clear. Acceptable: Thinness is recognized, and unevenness is slightly lacking in sharpness, but is judged to be practically usable. Impossible ... Thickness is terrible, unevenness lacks sharpness,
Those that cannot be used practically.

[0181]

[Table 12]

[0182]

[Table 13]

[0183]

[Table 14]

[0184]

[Table 15]

[0185]

[Table 16]

[0186]

[Table 17]

From the results of the drying test, it was found that the coating composition prepared by using the resin emulsion according to the present invention has a faster drying property than the coating composition prepared by using the resin emulsion for comparison in both the mill base method and the dry blend method. I understand. Furthermore, a comparison between the mill base method and the dry blend method shows that the dry blend method has faster drying properties. Therefore, the combination of the high-volatile, low-viscosity emulsion according to the present invention and the dry-blending coating method makes it possible to design an extremely quick-drying coating composition.

Next, from the result of the gloss value measurement, the coating composition prepared by using the resin emulsion according to the present invention was obtained as follows.
It can be seen that both the mill base method and the dry blend method have gloss values equal to or higher than those of the coating composition prepared from the comparative resin emulsion.

Further, from the results of the single-layer elastic paint application example, the paint composition prepared by using the resin emulsion according to the present invention has a more uneven pattern than the paint composition prepared by the comparative resin emulsion. It is recognized that the film is less thin, forms a sharp uneven pattern, and has no inferior properties in other coating properties.

Further, from the result of the application example of the multilayer elastic paint,
The coating composition prepared by using the resin emulsion according to the present invention has less thinning of the ball-blown pattern compared to the coating composition prepared by the comparative resin emulsion, and has other water resistance and alkali resistance. It can be seen that the physical properties of the coatings are equivalent.

[0191]

According to the process for producing a resin emulsion of the present invention, the particle size distribution can be intentionally controlled, the generation of agglomerates can be suppressed, and a resin emulsion having a wide particle size distribution can be produced by a one-stage emulsion polymerization method. Can be manufactured. The coating composition prepared by using this resin emulsion can obtain a product having a high solid content and a low viscosity. In addition, a coating method comprising applying this coating composition has an effect of being excellent in quick-drying property and having features such as elimination of a pattern and thinness at the time of thick film coating.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] June 19, 2000 (2006.1.
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

4. An aqueous medium in which an electrolyte substance is dissolved,
While adding vinyl monomer emulsified with a surfactant to the emulsion polymerization method for producing a resin emulsion according to claim 1, wherein.

5. The method according to claim 1, wherein the surfactant is an anionic surfactant,
The method for producing a resin emulsion according to any one of claims 1 to 4, wherein the resin emulsion is a mixture of an anionic surfactant and a nonionic surfactant.

6. vinyl monomer, (meth) those containing acryloyl groups one have a (meth) acrylic acid ester as essential components, the manufacture of the resin emulsion according to any one of claims 1 to 5 Law.

7. obtain a resin emulsion by one step emulsion polymerization method for producing a resin emulsion according to any one of claims 1-6.

8. A coating composition comprising, as an essential component, the resin emulsion obtained by the production method according to any one of claims 1 to 7 .

9. characterized by coating a coating composition according to claim 8, coating method.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful method for producing a resin emulsion, a coating composition containing the resin emulsion obtained by this method as an essential component, and a coating for applying the coating composition. About the law. More specifically, the present invention relates to a method for reducing the concentration of an electrolyte substance in an aqueous medium in which the electrolyte substance is dissolved ,
A method for producing a resin emulsion in which a vinyl monomer is emulsion-polymerized while increasing the surface activity ability, a coating composition containing a resin emulsion obtained by this manufacturing method as an essential component, and applying the coating composition It concerns the painting method.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

However, as a result of intensive studies, the present inventors have found that while the concentration of the electrolyte substance is intentionally lowered in an aqueous medium in which the electrolyte substance is dissolved , the surface activity is simultaneously reduced.
Emulsion polymerization of a vinyl monomer is carried out while increasing the abilities, so that even when the concentration of the electrolyte substance in the aqueous medium at the start of the emulsion polymerization exceeds 1% by weight, the emulsification by one-step reaction Even in the polymerization, a wide range of vinyl monomers can be used on a practical scale without impairing the polymerization stability, particle size distribution of resin emulsion, balance between non-volatile content and viscosity, amount of aggregates, etc. Can be controlled, the generation of aggregates is minimized, and the particle size distribution is significantly wider.
In addition, it has been found that a high-concentration, low-viscosity resin emulsion and a resin emulsion in which the particle size distribution is intentionally controlled can be produced.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

Furthermore, it is preferable that the present inventors have conductive Kaishitsu using a water-soluble polymerization initiators as part or all of the materials, the electrolyte concentration of the substance in the aqueous medium at the time of the emulsion polymerization initiator and 1 to 3 wt% That the persulfate is preferable as the electrolyte substance, and emulsion polymerization is carried out by dropping a vinyl monomer containing, as an essential component, a (meth) acrylate having one (meth) acryloyl group as an essential component. ,
It is preferable to decrease the electrolyte concentration in the aqueous medium over time, and as the surfactant capable of increasing the surfactant activity, an anionic surfactant or a mixture of an anionic surfactant and a nonionic surfactant is preferable. It has been found that the resin emulsion thus obtained can be suitably used for a coating composition, and that the obtained coating composition can be used for various coating methods.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

That is, the present invention provides: In an aqueous medium in which an electrolyte substance is dissolved, the concentration of the electrolyte substance is reduced, and the surface activity is increased.
A method for producing a resin emulsion, characterized in that a vinyl monomer is emulsion-polymerized while

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] 2. The method for producing a resin emulsion according to the above 1, wherein a water-soluble polymerization initiator is used as the electrolyte substance, and the concentration of the electrolyte substance in the aqueous medium at the start of emulsion polymerization of the vinyl monomer is 1 to 3% by weight.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

3. The method for producing a resin emulsion according to the above 1 or 2, wherein the electrolyte substance is a persulfate;

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Deleted

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011] 4 . The method for producing a resin emulsion according to the above 1 , 2, or 3 , wherein emulsion polymerization is performed while adding a vinyl monomer emulsified with a surfactant to an aqueous medium in which an electrolyte substance is dissolved,

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

5 . The method for producing a resin emulsion according to any one of the above 1 to 4 , wherein the surfactant is an anionic surfactant or a mixture of an anionic surfactant and a nonionic surfactant.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

6 . The method for producing a resin emulsion according to any one of the above 1 to 5 , wherein the vinyl monomer contains, as an essential component, a (meth) acrylic ester having one (meth) acryloyl group.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

7 . The method for producing a resin emulsion according to any one of the above 1 to 6 , wherein the resin emulsion is obtained by one-stage emulsion polymerization,

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

8 . A coating composition comprising, as an essential component, the resin emulsion obtained by the production method according to any one of the above 1 to 7 , and

[Procedure amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

9 . A coating method, characterized by coating the coating composition according to the above item 8 .

[Procedure amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. In carrying out the method for producing the resin emulsion of the present invention, various emulsion polymerization methods are used.
It is possible to have use. As the emulsion polymerization method, a thermal decomposition method using thermal decomposition of a polymerization initiator, a known oxidizing agent and a reducing agent,
Further, if necessary, a method such as a redox polymerization method using an acid or a metal ion can also be used.

[Procedure amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

[0018] Next, to illustrate the specific manufacturing method. Prior to the reaction, a vinyl monomer emulsified with a surfactant, preferably a vinyl monomer containing, as an essential component, a (meth) acrylic ester having one (meth) acryloyl group (hereinafter, this emulsified monomer) The resulting vinyl monomer is abbreviated as “pre-emulsion”.) The pre-emulsion is prepared, for example, by dissolving a surfactant in ion-exchanged water in advance in a stirring vessel, adding a vinyl-based monomer into this, and sufficiently stirring and emulsifying.

[Procedure amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Next, a reaction vessel for emulsion polymerization equipped with a stirring blade, a thermometer and a reflux condenser is prepared, and an aqueous medium is previously charged. The temperature is raised to the temperature required for the emulsion polymerization reaction, and a small amount of the pre-emulsion is added in order to form initial particles as necessary. If necessary, a surfactant or an emulsion for seeds may be used separately. Next, a required amount of the electrolyte substance and / or the polymerization initiator is charged and stirred to form initial particles as required. It is preferable to set the concentration of the electrolyte substance in the aqueous medium at this time to 1 to 3% by weight. Thereafter, dropping of the pre-emulsion and, if necessary, the polymerization initiator and the reducing agent are started. At that time, the concentration of the electrolyte in the aqueous medium in the reaction vessel decreases as the pre-emulsion, the polymerization initiator, and the dropping rate and the dropping amount of the reducing agent are intentionally adjusted. At this time, the emulsifier concentration is increased in parallel . Surprisingly, the particle size of the resulting emulsion changes extremely with time, and in a normal one-stage emulsion polymerization method, a large particle size distribution, a high non-volatile content, a low viscosity It becomes possible to produce an emulsion.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 157/00 C09D 157/00 // C08F 20/10 C08F 20/10 (72) Inventor Yoshihiro Okamoto Osaka 3-8-23 Gomonhigashi, Kumatori-cho, Sennan-gun 3-8-23 F-term (reference) 4D075 CA38 CA44 CA47 CB04 DB04 DB07 DB12 DB13 EA06 EA13 EB07 EB13 EB14 EB15 EB16 EB19 EB20 EB22 EB32 EB33 EB35 EB37 EB38 EB45 4J011 KB23 KA45 CH031 CH041 CH071 CH081 CH111 CH121 CH151 CH171 CL001 EA011 GA15 HA366 KA09 LA04 MA10 NA26

Claims (10)

[Claims] 1. An aqueous medium in which an electrolyte substance is dissolved,
A method for producing a resin emulsion, wherein a vinyl monomer is emulsion-polymerized while reducing the concentration of the electrolyte substance. 2. The resin emulsion according to claim 1, wherein a water-soluble polymerization initiator is used as the electrolyte substance, and the concentration of the electrolyte substance in the aqueous medium at the start of emulsion polymerization of the vinyl monomer is 1 to 3% by weight. Manufacturing method. 3. The method for producing a resin emulsion according to claim 1, wherein the electrolyte substance is a persulfate. 4. The process for producing a resin emulsion according to claim 1, wherein the vinyl monomer is emulsion-polymerized while increasing the surface activity. 5. An aqueous medium in which an electrolyte substance is dissolved,
The method for producing a resin emulsion according to any one of claims 1 to 4, wherein emulsion polymerization is performed while adding a vinyl monomer emulsified with a surfactant. 6. The surfactant, wherein the surfactant is an anionic surfactant,
6. The method for producing a resin emulsion according to claim 4, wherein the resin emulsion is a mixture of an anionic surfactant and a nonionic surfactant. 7. The resin emulsion according to claim 1, wherein the vinyl monomer contains, as an essential component, a (meth) acrylate having one (meth) acryloyl group. Law. 8. The method for producing a resin emulsion according to claim 1, wherein the resin emulsion is obtained by one-stage emulsion polymerization. 9. A coating composition comprising, as an essential component, the resin emulsion obtained by the production method according to claim 1. Description: 10. A coating method, comprising coating the coating composition according to claim 9.