JPS63120771A - Resin composition for water-based paint - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent whiteness, shelf stability, gloss, etc., consisting of an aq. binder and a specified non-film-forming polymer emulsion. CONSTITUTION:5-70% (by weight; the same applies hereinbelow) alpha,beta- ethylenically unsaturated carboxylic acid is emulsion-polymerized with 5-95% 1-8C alkyl (meth)acrylate, 0-50% arom. vinyl compd. and 0-50% other copolymerizable monomer at 0-100 deg.C to obtain a copolymer (a). 70-99.9pts.wt. mixture (l) of 0-10% alpha,beta-unsaturated carboxylic acid, 0.1-5% monomer having a phosphate group, 50-99.9% arom. vinyl compd. and 1-49.9% other copolymerizable monomer is emulsion-polymerized in the presence of 0.1-30pts. wt. component (a) to obtain a non-film-forming polymer emulsion (B) having a solid content of 20-60%. 100pts.wt. (on a solid basis) aq. binder (A) (e.g., a vinyl resin emulsion) is blended with 0.1-9,900pts.wt. component B and 0-300 pts.wt. pigment (C).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a new and useful resin composition for water-based paints, which provides excellent whiteness when formed into a film with a suitable binder, and which has other properties. The present invention relates to a resin composition for an aqueous paint containing fine particles of a non-film-forming polymer that has good affinity with the pigment when used with the pigment.

[Prior art and its problems] Conventionally, the above-mentioned resin composition for water-based paints uses monovinylidene aromatic as non-film-forming polymer fine particles, as disclosed in Japanese Patent Publication No. 4B-6524. Class 8
Those using emulsion particles with a particle size of 0.3 to 0.8 μm obtained by emulsion polymerization of 0 wt% or more and 20 wt% or less of other monomers, and those using JP-A-2007-100001, for which the present inventors previously applied for a patent. Disclosed in Publication No. 61-62510,
A monomer mixture having a solubility parameter difference of 0.1 or more from the above polymer in the presence of an emulsion obtained by emulsion polymerization of a polymerizable vinyl monomer and, if necessary, a polyfunctional crosslinkable monomer. It is known to use emulsion particles having small pores inside obtained by emulsion polymerization.

A problem with such prior art resin compositions for aqueous paints is that the whiteness of the non-film-forming resin emulsions is not satisfactory. For example, special public Sho 4B-6
JP-A-61- than that obtained according to No. 524.
Although the non-film-forming polymer fine particles obtained according to Publication No. 62510 have superior whiteness, the current situation is that this whiteness has not been utilized to replace titanium oxide, which is a conventional white pigment. . In addition, when the non-film-forming polymer fine particles in the prior art are applied as a water-based paint composition, they have insufficient affinity (miscibility) with other pigments used, and, for example, the composition does not have color. There were problems such as separation and poor gloss and sharpness.

[Means for Solving the Problems] In view of the above points, the present inventors have developed a method that has superior whiteness to non-film-forming polymer fine particles obtained by conventional techniques.
As a result of intensive studies in order to obtain a resin composition for water-based paints containing the fine particles, which has excellent stability and good gloss even when used in combination with other pigments, we found that A water-based paint composition containing fine particles as an essential component is
The present inventors have discovered that the present invention has satisfactory performance and have completed the present invention.

That is, the present invention comprises: (1) [1] Aqueous binder 100 type assembly (based on solid content); [2] (A) α, β, β-ethylene saturated carboxylic acid 5-
70 wt%, (meth)acrylic acid alkyl ester having a Cl-8 alkyl group, 5 to 95 wt%, aromatic vinyl compound 0 to 50 wt%, and 0 to sowt% of other monomers that can be copolymerized with the above components (ratio (A) based on the total amount of components) is emulsion polymerized, and - the above (^) component is 0.
．． (8) α, β-ethylenically unsaturated carboxylic acid 0 to 10 w in the presence of 1 to 30 parts
t%, phosphate ester group-containing monomer 0.1 to 5 wt%,
70 to 99.9@i part of a mixture consisting of 50 to 99.9 wt% of an aromatic vinyl compound and 0 to 49.9 wt% of a monomer copolymerizable with these (ratios are based on the total amount of component (B)). Non-film-forming polymer emulsion 0.1-99 obtained by emulsion polymerization to 1q
00 parts by weight (based on solid content);

First of all, the water-based binder that constitutes the present invention can be used without any particular problem as long as it is a binder for general water-based paint compositions such as lysine, flat, cloth, elastic, and metal paint compositions. Specific examples include vinyl resin emulsions, vinyl water-soluble resins, and vinyl resin aqueous dispersions. Such resins may be those obtained from vinyl monomers as described below according to known and commonly used manufacturing methods. Particular limitations include that the glass transition temperature of the above resins is 60°C or lower, and that the solid content concentration is 20 to 60 wt%.
It is preferable that

Next, the non-film-forming resin emulsion (2) will be explained.

Examples of α,β-ethylenically inert saturated carboxylic acids used to produce component (8) include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or citraconic acid anhydride. Carboxyl group-containing small bases or dicarboxylic acids such as unsaturated group-containing hydroxyalkyl ester monocarboxylic acids such as adducts of acid anhydride group-containing monomers such as maleic acid and itaconic anhydride with glycol: maleic anhydride, itaconic anhydride Examples include unsaturated monomers containing polyvalent carboxylic acid anhydride groups such as acids, and these monomers can be used alone or as a mixture of two or more. The amount used is 5 based on the total amount of component (A).
~70wt%.

Next, the (meth)acrylic acid alkyl ester having a C1-8 linear, branched or cyclic alkyl group constituting component (A) is, for example, methyl (meth)acrylate,
Examples include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate, and these can be used alone or in combination of two or more. As for the usage amount (^
) ranges from 5 to 95 wt% based on the total amount of components.

Examples of the aromatic vinyl compound include styrene or derivatives thereof such as styrene, α-methylstyrene, p-tert-butyl-styrene, and p-methylstyrene, which may be used alone or in combination of two or more thereof. The amount used is 0 to 50 wt% based on the total amount of component (A).

Other examples of monomers that can be copolymerized with these monomers include the following, which can also be used alone or in combination. The range that can be introduced into component (A) is 0 to 50 wt%.

First, examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, 3-hydroxypropyl(meth)
Acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4
-Hydroxyalkyl esters of (meth)acrylic acid such as hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate; polyesters such as maleic acid and fumaric acid; unsaturated group-containing polyhydroxyalkyl esters such as dihydroxyalkyl esters of monovalent carboxylic acids; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether;

Other (substituted) aromatic nucleus-containing (meth)acrylic acid esters such as benzyl (meth)acrylate: Diesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid, and Itamojisun: vinyl acetate, benzoic acid Vinyl, "Beoba" (vinyl ester manufactured by Shell)
Vinyl esters such as [Viscoat 8F, 8F
) i, 3F, 3FMJ (fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd. (11)), perfluorocyclohexyl (meth)acrylate, di-perfluorocyclohexyl fumarate, or N-1-propyl perfluorooctane Vinyl esters containing (per)fluoroalkyl groups such as sulfodiamidoethyl (meth)acrylate: vinyl chloride, vinylidene chloride, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene,
Olefins such as ethylene and propylene; (meth)
Acrylamide, N,N-dimethyl(meth)acrylamide, N-alkoxymethylated (meth)acrylamide, diacetone acrylamide, N-methylol(meth)acrylamide
Carbonamide group-containing monomers such as acrylamide; p-styrenesulfonamide, N-methyl-
p-styrenesulfonamide, N,N-dimethyl-p-
Monosteroids containing sulfonic acid amide groups, such as styrene sulfonamide; N,N-dialkylaminoalkyl (meth)acrylates, such as N,N-dimethylaminoethyl (meth)acrylate; or polyesters, such as maleic anhydride. Carboxylic acid anhydride group-containing monomers and N, N
- Tertiary amine group-containing monomers such as adducts with compounds having both an active hydrogen group and a tertiary amino group capable of reacting with polyhydric carboxylic acid anhydride groups such as dimethylaminopropylamine: (meth)acrylonitrile Cyano group-containing monomers such as: Phosphoric esters obtained by a condensation reaction of hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth)acrylic acid and phosphoric esters. Monomers having a sulfonic acid group such as 2-acrylamide-2=methylpropanesulfonic acid or organic amine salts thereof.

In addition, in order to improve the durability and solvent resistance of the final non-film-forming polymer particles, the following crosslinkable monomers are added as needed based on the total amount of component (A). Te 0
It is preferable to contain ~3 (hwt%).

Specific examples of crosslinkable monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate.
Monomers having two or more polymerizable unsaturated groups in the molecule, such as acrylate, divinylbenzene, trivinylbenzene, diallyl phthalate, etc.: vinyltriethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, 7 - There are hydrolyzable silyl group-containing monomers such as (meth)acryloyloxypropylmethyljethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, and γ-(meth)acryloyloxypropylmethyljethoxysilane. .

In order to produce component (A), the required amounts of each of the above monomer groups may be synthesized by a publicly known emulsion polymerization method in the presence of an emulsifier, a polymerization initiator, and water. Examples of emulsifiers used in this case include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances with surfactant properties such as acrylic oligomers. Anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. Typical nonionic emulsifiers include polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, and ethylene oxide-propylene oxide block copolymer, while anionic emulsifiers include alkylbenzene sulfone salts, Examples include alkyl sulfate alkali metal salts and polyoxyethylene alkylphenol sulfate alkali metal salts. In place of or in combination with the above-mentioned anionic emulsifier, a water-soluble oligomer made of polycarboxylic acid or sulfonate can also be used. Water-soluble polymeric substances such as polyvinyl alcohol and hydroxyethyl cellulose, which are sometimes used in emulsion polymerization, can be used as protective colloids. When these materials are used, the particle size of the emulsion obtained becomes large and the whiteness is good, but on the other hand, the water resistance and weather resistance of the coating film formed with the binder decreases, so the total amount of the emulsion increases. 5wt% or less, preferably 2wt%
% or less. The amount of the emulsifiers and the like to be used is about 0.1 to 10 wt% based on the total weight.

Next, the polymerization initiator is not particularly limited as long as it is commonly used in emulsion polymerization, but specific examples include water-soluble inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, etc. Persulfates such as cumene hydroperoxide, organic peroxides such as benzoyl peroxide: azobisisobutyronitrile,
Examples include azo initiators such as azobiscyanovaleric acid, and these may be used alone or in combination. The amount used is preferably 0.1 to 2 wt% based on the total amount of military mass. It goes without saying that a method known as a so-called redox polymerization method in which these polymerization initiators are used in combination with a metal ion and a reducing agent may also be used.

In the presence of water, preferably ion-exchanged water and an emulsifier, component (A) is mixed with the above-mentioned monomer mixture constituting component (^), either as it is or in an emulsified state, in a reaction vessel in bulk, in portions, or continuously. in the presence of the polymerization initiator at a temperature of 0 to 100°C, preferably 30 to 90°C. The ratio of total mass to water is such that the final solid content is 10 to 55 wt%, preferably 15 to 55 wt%.
It should be set within the range of %. Also, (A)
When adjusting the components, a so-called seed polymerization method may be used in which emulsion particles are preliminarily present in an aqueous phase and polymerized in order to grow or control the particle size of the resulting component (A).

In this way, a vinyl copolymer emulsion serving as component (A) can be prepared, and then in the presence of 0.1 to 30 parts by weight based on the solid content of the emulsion, 70 to 99% of the monomer mixture constituting component (8) is added. By additionally polymerizing .9 parts by weight, (B) was added to the surface of the emulsion particles of the (^) component.
A non-film-forming polymer fine particle emulsion, which is an essential component of the present invention, can be produced by depositing and polymerizing the components.

Monomers to be used in component (B) of the present invention include α,
β, β-ethylene saturated carboxylic acid 10 to iowt%, phosphate ester group-containing monomer 0.1 to 5 wt%, aromatic vinyl compound 50 to 99.9 wt%, and other monomers copolymerizable with these 0 to 49 .9wt% (more than that, the ratio is (B)
(component total set standard). Among these, the α,β-ethylenic saturated carboxylic acid aromatic vinyl compound may be appropriately selected from those detailed in the section of component (A).

In addition, monomers that can be copolymerized with these include the above-mentioned C
(meth)acrylic acid alkyl esters having 1-8 linear, branched or cyclic alkyl groups, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)
Acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3
-Hydroxyalkyl esters of (meth)acrylic acid such as chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate; di-hydroxyalkyl esters of polyhydric carboxylic acids such as maleic acid and fumaric acid. unsaturated group-containing polyhydroxyalkyl esters such as; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; (substituted) aromatic nucleus-containing (meth)acrylic acid esters such as benzyl (meth)acrylate;
Diesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid, and itaconic acid; vinyl esters such as vinyl acetate, vinyl benzoate, and "Beoba" (vinyl ester manufactured by Shell): [Viscoat 8
F, 8FM.

3F, 3F old (fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical ■), perfluorocyclohexyl (meth)acrylate, diperfluorocyclohexyl fumarate, or Nt-propyl perfluorooctane sulfodiamidoethyl Vinyl esters containing (per)fluoroalkyl groups such as (meth)acrylates:
Olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-alkoxymethylated (meth) Carribonamide group-containing monomers such as acrylamide, diacetone acrylamide, N-methylol (meth)acrylamide, etc.; p
- Sulfonic acid amide group-containing monomers such as styrene sulfonamide, N-methyl-p-styrene sulfonamide, N,N-dimethyl-p-styrene sulfonamide, etc.: N,N-dimethylaminoethyl (meth) N,N-dialkylaminoalkyl (meth)acrylates such as acrylates, or monomers containing polyvalent carboxylic acid anhydride groups such as maleic anhydride and polyvalent carboxylic acid anhydride groups such as N,N-dimethylaminopropylamine. Tertiary amino group-containing monomers such as adducts with compounds having both active hydrogen groups and tertiary amino groups capable of reacting with cyano group-containing monomers such as (meth)acrylonitrile: 2-acrylamide Examples include monomers having a sulfonic acid group such as -2-methylpropanesulfonic acid, and amine salts thereof.

What is characteristic of the present invention is that a phosphate group-containing monomer is used as an essential component as a raw material for component (B). The effect of introducing this monomer is that the non-film-forming polymer fine particles in the final composition have a good affinity with other pigments, so that color separation does not occur in the composition. The objective is to improve storage stability such as no generation of stains, gloss, and image clarity. Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate.
- Hydroxyl group-containing monomers such as hydroxypropyl (meth)acrylate, phosphoric acid or linear, branched or cyclic alkyl esters of phosphoric acid such as phosphoric acid monobutyl ester, phosphoric acid monobenzyl ester, and (substituted) aromatic Examples include esterified products with group esters. Specific examples of these products include [Light Ester PMJ]
(Kyoeisha Yushi @ product), rMR-260J (Oihe Kagaku ■ product), etc. The amount of the monomer used is preferably 0.1 to 5 wt%; if it is used more than this, the solubility with other monomers may deteriorate or lead to the generation of aggregates during emulsion polymerization. It is not appropriate for some reasons.

More preferably, in order to improve the durability and solvent resistance of the target product, a monomer having two or more polymerizable unsaturated bonds as described in the section of component (8) and/or hydrolyzable It is preferable to introduce a crosslinkable monomer such as a monomer containing a silyl group, and the amount used is within the range of 0 to 30 wt%.

In the polymerization of component (B), since it is contrary to the purpose of the present invention to produce a large number of particles of component (B) alone on a weight basis, the additional use of emulsifiers should be avoided as much as possible.
If necessary, the amount used of component (B) should be 5 wt% or less, preferably 2 wt% or less. Usage amount is 5wt
%, emulsion particles composed solely of component (B) will be produced as a by-product in the dormitory mat, and for example, when measuring the particle distribution, an emulsion having two peaks will be produced.

The polymerization initiator and the like are the same as described in the section of component (A).

The final solids concentration should be in the range of 20 to 60 wt%, preferably 30 to 55 wt%,
The particle diameter of the emulsion particles obtained is 0.3 to
The range is 1.5 μm. In addition, non-film-forming polymer particles are generally used by mixing them with the aqueous emulsion, water-soluble resin, or aqueous dispersion as the binder described above. Those that are difficult to solubilize or swell with basic substances such as morpholine and triethylamine are preferable, and more preferably, after contacting the fine particles with the basic substance, the volume of the fine particles changes by at most twice the volume of the fine particles before contact. Should. A substance that causes a volume change of more than twice as much will have a significant lack of stability in applications where it coexists with basic substances for a long period of time.
It cannot withstand use. The non-film-forming polymer emulsion, which is an essential component of the present invention, has a volume change of 2 after contact with a basic substance.
This stability against basic substances can only be achieved within the range described in the claims of the present invention.

Further, the non-film-forming polymer fine particle emulsion obtained according to the present invention can be powdered by a known and commonly used drying method. Spray drying, e.g. at a temperature of 100-250°C, 5
Tray drying at a temperature of 0 to 70°C or fluidized bed drying can be performed.

The particle size of the resulting non-film-forming resin powder is generally an aggregate of primary particles (fine particles having the same particle size as in emulsion) (secondary particles), but if necessary, dispersants such as emulsifiers,
Can be redispersed in water by adding protective colloids.

The ratio of component (1) to component (2) can range from 0.1 to 9,900 parts by weight of (1) to 100 parts (by weight) of (1) on a solid content basis.

Next, specific examples of the pigments in component (■) include heavy calcium carbonate, light calcium carbonate, magnesium carbonate, precipitated barium sulfate, mica, and titanium oxide, as well as kansui powder, powder, kaolin, clay, and fired pigments. leh, talc,
Silica sand, silica lime, ultrafine silica, white carbon, asbestos, pulp powder, dolomite powder, zinc white,
Inorganic pigments or fillers such as carbon black; organic pigments such as phthalocyanine, azo, and quinacridone pigments or their dispersion pigments. The amount of these pigments used is usually 0 to 300 parts by weight per 100 parts by weight of component (1).

Although the composition of the present invention can be obtained using these three components, various additives as shown below can also be blended.

Chisso Cizer C3-12 (Chisso ((3) product), butyl rubitol acetate, butyl cellosolve calpitol, hexylene glycol, cellosolve, dibutyl glycol phthalate, dibutyl phthalate, benzyl alcohol, diisopropyl succinate, Pyc
a194 (Atlas Chemical Industry
ries), [)aryad A (Dow Che
mical Co, ); and phthalate esters such as dioctyl phthalate, aliphatic dibasic acid esters such as isodecyl succinate and dioctyl adipate, and phosphate esters such as tricresyl phosphate. , glycol esters such as diethylene glycol benzoate, epoxy plasticizers such as epoxidized soybean oil, and various plasticizers such as chlorinated paraffins; various anionic and nonionic surfactants: pyrophosphoric acid, tripolyphosphoric acid , dispersants such as salts of phosphoric acid derivatives such as hexametaphosphoric acid, salts of polycarboxylic acids, salts of naphthalene sulfonic acid; drying agents such as mineral spirits and turpentine oil; ethylene glycol, propylene glycol, glycerin, methanol, etc. Antifoaming agents such as silicone-based or acrylic oligomers; and other preservatives are included, and the amount of these added is determined depending on the usage conditions and purpose.

[Effects of the Invention] The resin composition for water-based paints of the present invention has excellent whiteness due to the effect of the non-film-forming polymer particles, and therefore reduces the amount of conventionally used pigments, especially titanium oxide. It also has good affinity with other pigments used in combination with the fine particles, so aggregates are unlikely to form when stored for a long period of time.
Furthermore, the composition has excellent storage stability and does not cause color separation. The composition of the present invention can be used as general or industrial water-based paints for thin, flat, glossy, elastic, and metal paints, but is not particularly limited thereto.

[Example] Next, the present invention will be specifically explained with reference to Production Examples, Examples, and Comparative Examples. Hereinafter, all parts and percentages are based on mold temperature unless otherwise specified.

Production Example 1 50 parts of ion-exchanged water and 3.5 parts of emulsifier (2 parts of Emulgen 920 manufactured by Kao Corporation and Emal 1.5 parts of 10) was added and stirred well. Next, heat the reaction vessel and keep the internal temperature at 80°C and add acrylonitrile (AM>3 parts, n-butyl acrylate (BA) 6
and ethylene glycol dimethacrylate (EDH)
A) 1 part mixture and 0.25 ammonium persulfate
A mixture of 1 part and 5 parts of ion-exchanged water was added dropwise over 1 hour to cause a reaction, and the mixture was maintained at the same temperature for another 1 hour. Then, while maintaining the internal temperature at 80°C, add 10 parts of styrene (ST),
Methyl methacrylate (HMA) 13 parts, methacrylic acid ( ) fAA) 6 parts, divinylbenzene (DVB)
1 part of the mixture and a mixture of 0.25 parts of ammonium persulfate and 5 parts of ion-exchanged water were added dropwise over 1 hour to react, and the mixture was maintained at roughly the same temperature for 45 minutes. Thereafter, it was cooled to obtain an intermediate emulsion (A-1). The obtained emulsion had a solid content concentration of 40.1%, a DH of 2.5,
Average particle size 0.25 μm (Coulter Co
(measured value at UNTER N-4).

Production Example 2 50 parts of ion-exchanged water and 3.5 parts of emulsifier (2 parts of Emulgen 920 manufactured by Kao Corporation and Emal 1.5 parts of 10) was added and stirred well. Next, heat the reaction vessel, keep the internal temperature at 80°C, and add 5 parts of t-
A mixture of 4.5 parts of butyl methacrylate, 0.5 parts of γ-methacryloyloxypropyltrimethoxysilane, and a mixture of 0.25 parts of ammonium persulfate and 5 parts of ion-exchanged water were added dropwise over 1 hour to react, and the reaction was continued for another 1 hour. maintained at temperature. Then, while maintaining the internal temperature at 80°C, 3 parts ST, 20 parts HMA, 5 parts IAA, DV
A mixture of 2 parts B and 0.0 parts ammonium persulfate.
A mixture of 25 parts of ion-exchanged water and 5 parts of ion-exchanged water was added dropwise over 1 hour to cause a reaction, and the mixture was further maintained at the same temperature for 1 hour. after that,
After cooling, an intermediate emulsion (A-2) was obtained.

The obtained emulsion had a solid content concentration of 40.0% and I) H
2,4, the average particle diameter was 0.27 μm.

Production Example 3 60 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer.
The temperature was raised to 5°C. Then, 0.5 part of sodium dodecylbenzenesulfonate was dissolved in 10 parts of ion-exchanged water, and H)
fA 17.9 parts,) fAA 2 parts, E[)HAO01
and emulsify the mixture. A mixture of the emulsion, 0.2 parts of ammonium persulfate, and 10 parts of ion-exchanged water was dropped into the reaction vessel for 2 hours to effect polymerization. The reaction was completed by maintaining the same temperature for approximately 1 hour. Thereafter, it was cooled to obtain an intermediate emulsion (A-3). The obtained emulsion had a solid content concentration of 20.0%,
The pH was 2.1, and the average particle size was 0.24 μm.

Production Example 4 60 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer.
The temperature was raised to 5°C. Next, 0.5 part of sodium dodecylbenzenesulfonate is dissolved in 10 parts of ion-exchanged water, and a mixture consisting of 16.9 parts of H, 3 parts of t4AA, and 1 part of EOHAo is added and emulsified. Add 2 parts of the emulsion, a mixture of 0.2 parts of ammonium persulfate and 10 parts of ion-exchanged water.
The mixture is dropped into the reaction vessel mentioned above for a certain period of time to effect polymerization. The reaction was further maintained at the same temperature for 1 hour to complete the reaction. Thereafter, it was cooled to obtain an intermediate emulsion (A-4). The emulsion obtained had a solid content of 1 [20.2%, 1) tl
2.2, and the average particle diameter was 0.22 μm.

Production Example 5 (Production of non-film-forming polymer emulsion) 370 parts of ion-exchanged water and an intermediate emulsion (A- 1) Pour 100 parts and raise the temperature to 85°C. Next, dissolve 7 parts of sodium dodecylbenzenesulfonate in 90 parts of ion-exchanged water, ST 336.2
4 parts,) A mixture consisting of 8.36 parts of fAA i, 3.6 parts of DVB, and 1.8 parts of light ester PH is added and emulsified. A mixture of the emulsion, 3.6 parts of ammonium persulfate, and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out a reaction. Roughly at the same temperature 1
After holding for a period of time, it is cooled and the target object emulsion (A-
5) was obtained.

(8-5) had a solid content concentration of 40.2%, a pH of 2.7, and an average particle diameter of 0.53 μm.

Production Example 6 (same as above) 370 parts of ion-exchanged water and 100 parts of intermediate emulsion (A-2) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer. Raise the temperature to ℃. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 33
3 parts,) fAA 18 parts, γ-methacryloyloxypropyltrimethoxysilane 762 parts, Light Ester P
A mixture consisting of 1.8 parts of H is added and emulsified. The emulsion, 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water
The reaction mixture was dropped into the reaction vessel over a period of 2 hours to carry out the reaction. After roughly maintaining the same temperature for 1 hour, it was cooled to obtain the desired emulsion (A-6).

(A-6) was prepared at a solid content concentration of 40.4%, pH of 2.5, and average particle diameter of 0.54 μm.

Production Example 7 (same as above) 190 parts of ion-exchanged water and 300 parts of intermediate emulsion (A-3) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer. Raise the temperature to ℃. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 32
A mixture consisting of 0.62 parts of HAA, 11.9 parts of HAA, 86.8 parts of DV, and 0.68 parts of light ester PH is added and emulsified. A mixture of the emulsion, 3.4 parts of ammonium persulfate, and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out a reaction. After maintaining the same temperature for another 1 hour, it was cooled and an emulsion of the target object (
A-7) was obtained.

(A-7) has a solid content concentration of 40.0% and a pH of ? , 6. The average particle diameter was 0.47 μm.

Production Example 8 (same as above) 270 parts of ion-exchanged water and 200 parts of intermediate emulsion (A-4) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer. Raise the temperature to ℃. Next, dissolve 6 parts of sodium dodecylbenzenesulfonate in 90 parts of ion-exchanged water, and add ST 31.
9.68 copies,) IAA 19.8 copies, DVB 18 copies,
A mixture consisting of 2.52 parts of light ester P)f is added and emulsified. The emulsion and ammonium persulfate3.
A mixture of 6 parts of ion-exchanged water and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out the reaction. After roughly maintaining the same temperature for 1 hour, it was cooled to obtain the desired emulsion (A-8). (A-8) has a solid content concentration of 40.
2%, pH 2.5, and average particle size 0.48 μm.

Comparative Production Example 1 370 parts of ion-exchanged water and 100 parts of intermediate emulsion (A-1) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer, and the temperature was raised to 85°C. Increase temperature. Next, 7 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 33
6.24 parts,) fAA 18.38 parts, [)VB3.6
and emulsify the mixture. A mixture of the emulsion, 3.6 parts of ammonium per5A acid, and 80 parts of ion-exchanged water was dropped into the reaction vessel over a period of 2 hours to carry out a reaction. After roughly maintaining the same temperature for 1 hour, it was cooled to obtain a comparative emulsion (B-1). (B-
1) had a solid content concentration of 40.1%, DI+2.7, and average particle diameter of 0.51 μm.

Comparative Production Example 2 370 parts of ion-exchanged water and 100 parts of intermediate emulsion (^-2) were charged into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet pipe, and thermometer, and heated to 85°C. Increase temperature. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 32
A mixture consisting of 7.6 parts, 18 parts of iAA, and 7.2 parts of γ-methacryloyloxypropyltrimethoxysilane is added and emulsified. A mixture of the emulsion, 3.6 parts of perFArli ammonium, and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out the reaction. After roughly maintaining the same temperature for 1 hour, it was cooled to obtain a comparative emulsion (B-2). (B-2) has a solid content concentration of 40.0%, pH 2.6, and an average particle diameter of 0.56 μm.
Met.

Comparative Production Example 3 For stirring, 190 parts of ion-exchanged water and 300 parts of intermediate emulsion (A-3) were charged into a reaction vessel equipped with a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer, and the mixture was heated to 85°C. Increase temperature. Next, 5 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 32
A mixture consisting of 0.62 parts of HAA, 11.9 parts of HAA, and 6.8 parts of DVB is added and emulsified. A mixture of the emulsion, 3.4 parts of ammonium persulfate, and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out a reaction. After further maintaining the same temperature for 1 hour, it was cooled to obtain a comparative emulsion (B-3). (B-3) has a solid content concentration of 40.1%, a pH of 2.6, and an average particle size of 0.49.
It was μm.

Comparative Production Example 4 270 parts of ion-exchanged water and 200 parts of intermediate emulsion (A-4) were charged into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet pipe, and thermometer, and heated to 85°C. Increase temperature. Next, 6 parts of sodium dodecylbenzenesulfonate was dissolved in 90 parts of ion-exchanged water, and ST 31
8.6 parts), 19.8 parts of IAA, and 18 parts of DVB are added and emulsified. A mixture of the emulsion, 3.6 parts of ammonium persulfate, and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out a reaction. After roughly maintaining the same temperature for 1 hour, it was cooled to obtain a comparative emulsion (B-4). (G4) has a solid content concentration of 40.0%, pl+2.6, and an average particle size of 0.51.
It was μm.

Examples 1 to 5 and Comparative Examples 1 to 5 Each emulsion (19) prepared in Production Examples and Comparative Production Examples
A-5) to (8-8) and (B-1) to (B-4) as a binder emulsion VONCOA EC-8
80 (Dainippon Ink Chemical Industry viJ product), hydroxyethyl cellulose as a thickener, and if necessary, the titanium oxide paste listed in Table 1, and the dispersed pigment listed in the same table, and stirred until the viscosity becomes uniform. It was made into paint. It was then applied onto a glass plate with a 6 mil applicator, dried for one day at room temperature, and the gloss value was measured. The results are shown in Table-1. In addition, in order to examine the storage stability of the above paint, it was sealed tightly and left in a constant temperature and humidity machine at 50°C for one month. Furthermore, in order to evaluate the storage stability in the presence of a basic substance, 14% ammonia water was added in the amount shown in Table 1, and the particle diameter was measured after 11 months at 50'C. The results are also shown in the same table.

(Left below) $1) 70% aqueous dispersion of rutile titanium oxide *2) Dispersion Blue JS[)-6018J (manufactured by Dainippon Ink & Chemicals) *3) Dispersion Yellow rsD-4002J (
(manufactured by Dainippon Ink & Chemicals) Umbrella 4) (8-5) ~ (A-8), (B-1) ~ (B-4)
) and titanium oxide paste, pigment body vim degree when solid content of dispersed pigment is used as pigment *5) 60' cross value by Murakami gloss meter *5) 5
After being left in a constant temperature and humidity chamber at 0°C for one month, the evaluation is 01 for the presence or absence of color separation. If there is no color separation, then -8) and (B-1) ~
Add 7.5 parts of 14% ammonia water to each 100 parts of (B-4), stir well, and leave in a constant temperature and humidity oven for 1 month at 50°C with a tightly stopper ◎; Particle size change is initial in terms of volume. As shown in Table 1, the composition of the present invention It has excellent storage stability and does not cause color separation even when used in combination with various organic and inorganic pigments.

Claims (1)

[Claims] (1) [1] 100 parts by weight of an aqueous binder (based on solid content), [2] (A) 5 to 5 α,β-ethylenically unsaturated carboxylic acids
70 wt%, (meth)acrylic acid alkyl ester having a C_1_-_8 alkyl group, 5 to 95 wt%, aromatic vinyl compound 0 to 50 wt%, and other monomers that can be copolymerized with the above components 0 to 50 wt% (ratio (based on the total amount of component (A)) is subjected to emulsion polymerization, and 0.
In the presence of 1 to 30 parts by weight, (B) 0 to 10 w of α,β-ethylenically unsaturated carboxylic acid
t%, phosphate ester group-containing monomer 0.1 to 5 wt%,
Emulsify 70 to 99.9 parts by weight of a mixture consisting of 50 to 99.9 wt% of an aromatic vinyl compound and 0 to 49.9 wt% of a monomer copolymerizable with these (ratios are based on the total amount of component (B)). Non-film-forming polymer emulsion obtained by polymerization 0.1-990
0 parts by weight (based on solid content); [3] A resin composition for an aqueous paint, comprising: [3] pigments if necessary.