JPS60223873A - Water based paint composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent hiding power, gloss, water resistance, etc., consisting of a non-film-forming vinyl resin emulsion and a film-forming aq. resin. CONSTITUTION:A copolymer emulsion obtd. by emulsion-copolymerizing a polymerizable vinyl monomer (a) and a polyfunctional crosslinking monomer (h) is used as a seed. 99.9-10pts.wt. polymerizable vinyl monomer (c) which is different in solubility parameter from component (a) by 0.1 or above and 0-50pts.wt. polyfunctional crosslinking monomer (d) are emulsion-polymerized in the presence of 0.1-90pts.wt. said copolymer emulsion to obtain an emulsion (A) contg. 10-75wt% non-film-forming vinyl resin having a glass transition temp. of 40 deg.C or above, a particle size of 0.1-5.0mu and internal cells of 0.01-1.0mu. Component A and an emulsion (B) contg. 5-70wt% film-forming aq. resin having a glass transition temp. of 60 deg.C or below obtd. by polymerizing at least one polymerizable vinyl monomer are blended together in a weight ratio of A:B of 1:100-100:1 on a solid basis.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating composition that provides a coating film with excellent hiding properties, gloss, water resistance, etc., and also has excellent stability.

For example, Australian Patent No. 45
This method has been proposed in the specification of No. 5277 and the like.

That is, an aqueous pigment dispersion is dispersed into droplets and suspended in an unsaturated polyester solution containing an unsaturated monomer such as styrene,
The resulting suspension is dispersed in water in the form of beads, which are then polymerized and further stabilized by the addition of a water-soluble polymer, such as partially hydrolyzed polyvinyl acetate, containing core-shaped resin particles. or an improved version of the above composition using an unsaturated polyester resin having N IJ ethylene oxide chains without adding a water-soluble polymer (4V
29485) has been proposed.

However, although these coating compositions have excellent hiding properties, they have the drawback of producing coatings with no visible gloss.

As a result of intensive research into a water-based paint composition that does not have the above-mentioned drawbacks and has excellent paint properties, the present inventors have found that a core-shaped non-film-forming vinyl resin particle emulsion, that is, a core-shaped non-film-forming vinyl resin particle emulsion; 6j5, preferably a non-film-forming vinyl resin emulsion (1) that is hollow or contains a solvent in the core, and a film-forming aqueous resin (II
) provides an aqueous paint composition comprising:

The non-film-forming vinyl resin emulsion used in the present invention contains core-shaped resin particles having small pores (microvoids) inside. The small pores of the particles may be cavities, or water or a volatile solvent may be present, and if water or a solvent is present, the water or volatile solvent inside evaporates during drying, and the small pores Non-film-forming vinyl resin particles are formed. Further, the above particles usually have a particle size of 0.1 to 5.0 microns, preferably 0.2 to 1.0 microns, and the small pores (micro voids) inside them are usually 0.
．． 01-1.0 micron, preferably 002-0,5
It has a diameter of microns.

The solid content concentration of the non-film-forming vinyl resin emulsion in the present invention is not particularly limited, but is generally from 5 to 70% by weight, preferably from 20 to 60% by weight. The amount required is 5
If it is less than 70% by weight, the hiding property will be insufficient, and if it exceeds 70% by weight, it will be difficult to manufacture.

Further, the non-film-forming vinyl resin emulsion used in the present invention can be produced by various methods. Typical manufacturing methods are listed below.

(1) Copolymer emulsion (C) obtained by emulsion copolymerization of a polymerizable vinyl monomer (A) and a polyfunctional crosslinkable monomer (B) by a normal method 0.1 to 90 weight part is the seed particle, and the difference in solubility parameter from the monomer (4) is 0.
．． Polymerizable vinyl monomer (D) i99.9 or more, which is 1 or more
10 parts by weight, polyfunctional crosslinkable monomer (E) t-0 to 5
A non-film-forming vinyl resin emulsion with hiding properties obtained by emulsion polymerization of 0 parts by weight is produced. The emulsion particles produced by this method are 01 to 3.0μ
m allows for hiding performance without reducing gloss.

The polymerizable vinyl monomer (4) used in this method is:
Methyl-, ethyl-, globi-, n-butyl-1l-
(meth)acrylics such as gutyl-1t-butyl-1n-amyl-1l-7mil-, hexyl-, octyl-, nonyl-, decyl-, dodecyl-, octadecyl-, cyclohexyl-, phenyl- or benzyl (meth)acrylate. Acid esters; vinyl esters such as vinyl acetate, vinyl gropionate, vinyl butyralate or "vinyl persate"; methyl-, ethyl-,
Vinyl ethers such as propyl, butyl, amyl, or hahexyl vinyl ether; Vinyl cyanides such as acrylonitrile; Vinyl halides such as vinyl chloride or vinylidene chloride: ° or maleic e
- dialkyl esters of saturated dibasic acids such as dialkyl esters of malic acid or itaconic acid, olefins such as styrene and vinyltoluene; monoenes and dienes such as ethylene and butadiene, α, β
~Unsaturated acids such as ethylenically unsaturated caldicic acid, vinyl sulfonic acid or styrene sulfonic acid or their salts: glycidyl compounds such as (methyl)glycidyl (meth)acrylate: (meth)acrylamide or their N-methylolated products; Alkoxylated products thereof; α, β-ethylenically unsaturated monomers containing a sidine group, such as vinyltrichlorosilane or vinyltriethoxysilane; or α, β-ethylenically unsaturated monomers containing a hydroxyl group, such as β-hydroxyethyl (meth)acrylate. There are monomers, and these can be used alone or in combination of two or more.

As the polyfunctional crosslinkable monomer (B), ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, trivinylbenzene , diallyl phthalate, ethylene glycol diacrylate), 1,3-butylene glycol diacrylate, and the like.

Furthermore, the polymerizable vinyl monomer CD) has a solubility difference of 0.1 or more, preferably 0.1 to 10 The monomer (A) is selected from among the monomers (A).

Of course, two or more types of polymerizable vinyl monomers (D) may be used. Note that the solubility parameters are, for example, Small,
P,S,,J,Appl,Chem,, 3,7
5 (1973), it is calculated as δ=d·8017M.

The polyfunctional crosslinkable monomer (E) copolymerizable with the polymerizable vinyl monomer (E) may be the same as the polyfunctional crosslinkable monomer used for the seed particles.

The amount of the polyfunctional crosslinkable monomer used to produce the copolymer emulsion (C) containing the seed particles is O to 50 parts by weight based on the total 100 parts by weight of the polymerizable vinyl monomer figure. , preferably 0 to 30 parts by weight. Further, the amount of the polyfunctional crosslinkable monomer (E) used after forming the seed particles is preferably 0 to 50 parts by weight based on the total 100 parts by weight of the polymerizable vinyl monomer (6), and particularly preferably 0-3
It is 0 parts by weight. In addition, such a polyfunctional crosslinkable monomer (E
) improves the solvent resistance of the non-film-forming vinyl resin particles, but if the amount exceeds 50 parts by weight, production becomes difficult. During production, emulsifiers and catalysts are usually used. Examples of emulsifiers that can be used include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances with surfactant properties such as acrylic oligomers.
One species or two or more species can be used in combination. Among these, nonionic and anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. As a nonionic emulsifier, polyoxyethylene alkylphenol ether, +tel
Any of the commercially available nonionic emulsifiers such as J-oxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, and ethylene oxide-propylene oxide block copolymer can be used.As anionic emulsifiers, alkylbenzene sulfonic acid alkali salts, alkyl Any of commercially available anionic emulsifiers such as sulfate alkali salts and polyoxyethylene alkylphenol sulfate alkali salts can be used.

Furthermore, it is also possible to use water-soluble oligomers in place of or in combination with the above-mentioned anionic emulsifiers. It is also possible to obtain so-called soap-free emulsion compositions.

In addition, protective colloids often used in emulsion polymerization can also be used. Examples of protective colloids include water-soluble polymeric substances such as polyvinyl alcohol, hydroxyethyl, and cellulose. When these protective colloids are used in emulsion polymerization, the particle size of the obtained emulsilon becomes large and the hiding property becomes good, but the presence of these protective colloids reduces the water resistance and weather resistance of the mixed coating film. Therefore, when using 100 parts by weight of total leather,
Emulsifiers are always used during the production of the copolymer emulsion (C) that serves as seed particles, but they may or may not be added during subsequent polymerization, and it is usually better not to add them. preferable.

The amount of emulsifier used is not particularly limited, but is usually about 0.1 to 10 parts by weight per 100 parts by weight of the total leather mass.

In addition, as a catalyst, any catalyst commonly used in emulsion polymerization may be used; representative examples include water-soluble inorganic peroxides or persulfates such as hydrogen peroxide and ammonium persulfate; cumene; Hydroperoxide, Pennzoylno! -Organic peroxides such as oxides: azo compounds such as azobisisobutyronitrile, etc.; these may be used alone or as a mixture of two or more. The amount used is 01~
It is about 2%.

In addition, these catalysts, metal ions, reducing agents, and the various monomers described above may be added all at once, in parts, or by continuous dropwise addition, and the presence of the catalysts described above may be added. Below, 0~100℃, practically 30~9
It is polymerized at a temperature of 0°C.

(11) A stable water-in-oil (WLO) emulsion is prepared by stirring a polymerizable vinyl monomer, water, and a lipophilic emulsifier, and this is dispersed in water using a suitable hydrophilic emulsifier. A stable W10/W type composite emulsion is obtained. The volume fraction of the internal water phase in a liquid composite emulsion is usually 0.10 to 0.
．． 95, preferably 0.3 to 0.9.

Further, the concentration of the lipophilic emulsifier is usually 0.1% by weight or more, preferably 1% by weight or more. In contrast, the concentration of the hydrophilic emulsifier is usually less than 10% by weight, preferably less than 5M. In addition, the weight ratio of lipophilic emulsifier/hydrophilic emulsifier is 0.
．． 1 or more, preferably 1 or more.

A non-film-forming vinyl resin emulsion is produced by polymerizing the polymerizable vinyl monomer in the composite emulsion.

The above-mentioned lipophilic emulsifiers include sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, glycerol monooleate, polyoxyethylene monooleate, sorbitan monolaurate, polyoxypropylene-polyoxyethylene-cetyl alcohol, Examples include ethylene glycol monooleate and propylene glycol monooleate. Other HLB
All emulsifiers with a low, preferably less than 13, fall into this category.

The polymerizable vinyl monomer is mainly the same as the polymerizable vinyl monomer used in (1) above, and the polyfunctional crosslinkable monomer (B) can be used in combination.

Examples of hydrophilic emulsifiers include commercially available anionic emulsifiers such as alkylbenzene sulfonic acid alkali salts, alkyl sulfate alkali salts, alkyl sulfate alkali salts, polyoxyethylene alkylphenol sulfate alkali salts, and nonionic emulsifiers with a high HLB, preferably 13 or more. Emulsifiers such as emulsifiers, cationic emulsifiers, other reactive emulsifiers, acrylic oligomers, and other substances having surfactant ability can be used, and these can be used alone or in combination of two or more. Among these, anionic emulsifiers and nonionic emulsifiers are preferred because they form stable W10//w type composite emulsions. It is also possible to use protective colloids often used in emulsion polymerization, ie, those similar to those shown in the production method (1) above, as the hydrophilic emulsifier.

When carrying out normal emulsion polymerization of the monomers in the W70/W composite emulsion, a catalyst is used to carry out the emulsion polymerization to produce a non-film-forming polymer emulsion at room temperature that has concealment properties and has an internal aqueous phase within the particles. can do. Examples of such catalysts include those used in the method (1) above. Further, the polymerization temperature during emulsion polymerization is preferably in the range of 0 to 90°C.

(11D The copolymer emulsion (C) from the method (1) above is used as seed particles, and then the seed particles are swollen with an insoluble solution in water, and a polymerizable vinyl monomer is added to the seed particles. (F
) 99 to 10 parts by weight, polyfunctional crosslinkable monomer (G) 0.
A non-film-forming vinyl resin with masking properties is produced by adding 1 to 50 parts of the seed particles to further swell the seed particles, followed by emulsion polymerization to produce a solvent-containing emulsion, and then distilling off the solvent under reduced pressure. Manufacture an emulsion.

The copolymer emulsion (C) is as shown in the production method (1) above.

As the non-polymerizable solvent insoluble in water, aliphatic hydrocarbon solvents such as propane, butane, hexane, hegetane, and octane, and aromatic organic solvents such as toluene and xylene are used.

Polymerizable vinyl monomer (F), polyfunctional crosslinkable monomer (G
) is also the one used in the manufacturing method of (1) above.
In this production method, it is preferable to use an emulsifier and a catalyst, and those used in the above (1) can be used in the same manner.

In addition, the various monomers described above may be added all at once, in portions, or continuously by dropwise addition, usually in the presence of the catalyst described above at 0 to 100°C. is polymerized at a temperature of 30-90°C.

The polymer emulsion containing a solvent is a non-film-forming emulsion at room temperature that has masking properties as it is, but preferably the solvent is distilled off under reduced pressure to reduce the solid content to 10 to 75% by weight, preferably 20% by weight. The effect is doubled when the amount is ~65% by weight.

In the non-film-forming vinyl resin emulsion used in the present invention, the glass transition temperature (Tg) of the resin component is preferably 40°C or higher, particularly preferably 60°C or higher. It takes T
If g is less than 40°C, the hiding property will be insufficient and there is a risk of film formation. In addition, if the Tg is around 60°C, there is no fear of film formation at room temperature, and hiding properties can be exhibited.In addition, the non-film-forming vinyl resin emulsion has resin particles that have small pores (microvoids) inside. Because of this,
Even if water or a volatile solvent is present in the coating, it evaporates during drying and exhibits hiding properties due to diffuse reflection of light after the coating film is formed.

Note that it can be easily confirmed whether the core-shaped resin particles of the non-film-forming vinyl resin emulsion have small pores. For example, small pores can be confirmed using transmission and scanning electron microscopes themselves, and small pores can also be easily confirmed in the coating film after the paint is mixed. It is also possible to measure the specific gravity of the emulsion.

Among the above-mentioned methods for producing a non-film-forming vinyl resin emulsion, the above-mentioned method (1) is particularly preferred, followed by the above-mentioned Qill method.

A film-forming water-based resin to be blended with the non-film-forming vinyl resin emulsion may be used as a binder for general water-based paint compositions such as thin, flat, glossy, elastic, and metal. based resin emulsion,
Vinyl water-soluble AT fats, vinyl resin aqueous dispersions, etc. are used. Such resins are usually obtained by polymerizing at least one kind of polymerizable vinyl monomer, and examples of the polymerizable vinyl monomer include aromatic resins such as styrene, methylmethylene, and α-methylstyrene. Alkenyl compound; methyl, ethyl, propyl-1n-butyl-1l-butyl-1t-butyl-1n-amyl, i
-amyl-, hexyl-, octyl-, nonyl-, decyl-, dodecyl-, octadecyl-, cyclohexyl-
(meth)acrylic acid esters such as phenyl- or benzyl (meth)acrylate; vinyl esters such as vinyl acetate, vinyl zolopionate, vinyl butylade or "vinyl parzate"; methyl-,
vinyl ethers such as ethyl, propyl, butyl, amyl or hexyl vinyl ether; vinyl cyanides such as acrylonitrile; vinyl halides such as vinyl chloride or vinylidene chloride; Kine-saturated dihydrochloric acid dialkyl esters such as dialkyl esters; α,β-ethylenically unsaturated carboxylic acids; unsaturated acids such as vinylsulfonic acid or styrenesulfonic acid; or salts thereof; glycidyl compounds such as (methyl)glycidyl (meth)acrylate; : (meth)acrylamide or its N-methylolated product or its alkoxylated product; silane group-containing α,β-ethylenically unsaturated monomer such as vinyltrichlorosilane or vinyltriethoxysilane; or β-hydroxyethyl (meth) Hydroxyl group-containing α,β-ethylenically unsaturated monomer such as acrylate; ethylene glycol dimethacrylate, 1.3
-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, etc. They can be used alone or in combination of two or more.

Among such film-forming water-based resins, vinyl resin emuls)
In the production of III, the above monomers are added all at once, in portions, or continuously dropwise, and polymerized at a temperature of 0 to 100°C, preferably 30 to 90°C, usually in the presence of an emulsifier and a catalyst. I can do it all the time. The emulsifier and catalyst used in this case may be those used in the production of non-film-forming vinyl resin emulsions. In addition, the production of vinyl water-soluble resin involves polymerizing hydrophilic monomers of the above-mentioned polymerizable vinyl monomers and other monomers in a water-soluble organic solvent such as methanol or ethanol at 80 to 150°C. It is done by doing. Further, the vinyl resin aqueous dispersion is produced by polymerizing the above-mentioned water-soluble resin by reducing the amount of the hydrophilic monomer, and then dispersing it in water.

The glass transition temperature (Tg) of the resin component of the film-forming vinyl resin Emulsilin used in the present invention is 60°C or lower, preferably 40°C or lower. Moreover, the solid content is 5 to 70% by weight, preferably 20 to 60% by weight. If it is less than 5% by weight, it is economically disadvantageous, and if it is more than 70% by weight, polymerization is difficult.

In addition, the Emulsiro/ contains Chisso Cizer C8-12 (manufactured by Chisso Corporation), butyl calpitol acetate, butyl cellosolve, calpitol, hexylene glycol,
Cellosolve, cyphthyl glycol phthalate, sibutyl phthalate, benzyl alcohol, diiso f0 virconolate, pyca194 (Atlas Ch
emlcal Industries) + Dalya
d A (Dow-Chemical Co +) or other film-forming agent in an amount of 0.1 parts by weight per 100 parts by weight of the solid content of Emulzolone.
About 10 parts by weight may be added.

The water-based coating composition of the present invention comprises the non-film-forming vinyl resin emulsion (1) and the film-forming vinyl resin emulsion (1).
If), and the solid content weight ratio of the former and the latter is usually 1.
:100-100:1, preferably 1:100-10:
It is 1. Such non-film-forming vinyl resin emulsion (
When the solid content ratio of 1) is less than 1, the hiding property is lowered, and when it exceeds 100, the physical properties of the coating film tend to be insufficient.

Further, the aqueous coating composition of the present invention may contain titanium oxide, which exhibits the effect of further improving the hiding property. The amount of titanium oxide to be blended is usually [solid content weight in (1) above]/weight of soil titanium oxide above (solid content weight in IQ = 1/Z00 to 10V1, preferably 1/100 to 10/1). It is.

Furthermore, other paint additives can be incorporated into the composition of the present invention. Other paint additives include heavy calcium carbonate, light calcium carbonate, cold water powder, powder,
Kaolin, clay, calcined clay, talc, silica sand, silica lime, bentonite, asbestos, ) 9 lupus powder, white carbine, ultrafine anhydrous silica, dolomite powder,
Fillers or pigments such as magnesium carbonate, precipitated barium sulfate, lithopone, zinc white, iron oxide, carbon black, chromium oxide, ultramarine blue, etc. Phthalate esters such as dibutyl niatalate and dioctyl phthalate, isodecyl conolyphosphate, adipine Aliphatic dibasic acid esters such as dioctyl acid, phosphoric acid esters such as tricresyl phosphate, glycol esters such as diethylene glycol benzoate, epoxy plasticizers such as epoxidized soybean oil, chlorinated pants, Various plasticizers such as polyoxyethylene alkylphenyl ethers and polybutene, various nonionic surfactants: salts of condensed phosphoric acid such as birophosphoric acid, tripolyphosphoric acid, hexameta + heptaphosphoric acid, and polycaldene. Dispersing agents such as acid salts and naphthalene sulfonates; Drying regulators such as mineral spirits and turpentine oil; Freezing or MS stabilizing agents such as ethylene glycol, phlopylene gellicol, glycerin, and methanol; Antifoaming agents or preservatives The amount of these compounds to be added is appropriately determined depending on the purpose.

Therefore, the water-based paint composition of the present invention can produce a coating film with excellent hiding properties, gloss, water resistance, etc. without adding extender pigments, and in particular, adding titanium oxide further promotes hiding properties. Moreover, it is possible to produce a high-gloss coating film.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, in which all parts and parts are based on weight unless otherwise specified. In addition, all polymerizations are performed using an inert gas (
N2) Conducted under atmosphere.

[Production of non-film-forming vinyl resin emulsion] Production row A
(Production method of (1) above) (A-1) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of water and 5 parts of an emulsifier (3 parts of Emulgen 120 manufactured by Kao Atlas Co., Ltd.) were added. 1 part and 2 parts of Emal 20A) and stirred well. Next, the reaction vessel was heated, and the internal temperature was maintained at 80°C, and a mixture of 14 parts of t-butyl methacrylate, 1 part of acrylic acid, 0.5 parts of glycidyl methacrylate, and 0.25 parts of ammonium persulfate was added.
A mixture of 1 part and 5 parts of water was injected for about 1 hour to react.
Let it mature for another hour. After that, keep the internal temperature at 80℃,
A mixture of 82 parts of p-methylstyrene, 2 parts of acrylic acid, 0.5 parts of glycidyl methacrylate, and a mixture of 0.25 parts of ammonium persulfate and 5 parts of water were injected and reacted over about 1 hour, and further aged for 45 minutes. Ta. After that, it was cooled, and 3.0 parts of 25% ammonia aqueous solution was added.
．． Adjusted to 5.

The obtained emulsion had a solid content concentration of 48.0 cm and a viscosity of 1
0cp8 (BM type rotational viscometer rotor A1, rotation speed 6O
rpm, value at 25°C), pH 8.5, average particle diameter 0.3 to 0.4 μm measured using an Iu particle microscope. The average diameter of the id was 0.1 to 0.2 μm.

This emulsion is A-1! :do.

(A-2) In a reaction vessel similar to A-1 above, 100 parts of water and 7 parts of emulsifier (3 parts of Emulgen 920 and 2 parts of Emulgen 120)
and 2 parts of Hitenol N-08) and lower the internal temperature to 70℃.
A mixture of 0.2 parts ammonium persulfate and 5 parts water, kept at
A solution of a mixture of 0.2 parts of sodium pyrosulfite and 5 parts of water, 20 parts of styrene, 20 parts of 1-butyl methacrylate, and 1 part of ethylene glycol dimethacrylate was injected over about 1.5 hours to react. Aged for 1 hour. Styrene 50 was added to the resulting seed particle emulsion.
8 parts of n-butyl acrylate, 1 part of ethylene glycol dimethacrylate, 0 ammonium persulfate
．． A mixture of 2 parts and 5 parts of water and pyrosulfite) IJ
A mixture of 0.2 parts of aluminum and 5 parts of water was injected for 2 hours each, reacted at 80°C, and further aged for 45 minutes. Thereafter, it was cooled and 0.1 part of a 25% ammonia aqueous solution was added to adjust the - to 8.7.

The obtained emulsion had a solid content concentration of 47% and a viscosity of 15c.
ps (BM type rotational viscometer rotor A1, rotation speed 6Orp
m, value at a temperature of 25°C), pH 8.7, and the average particle diameter of the particles measured using an electron microscope is 0.3 to 0.4 μm. The average diameter of the id was 0.05 to 0.15 μm. This emulsion is designated as A-2.

(A-3) In a reaction vessel similar to A-2 above, 100 parts of water and 7 parts of emulsifier (5.0 parts of Emuldan 120i and Hytenol N-
08), keeping the internal temperature at 70℃, and adding a mixture of 0.2 parts of ammonium persulfate and 5 parts of water, pyrosulfite).
A mixture of 0.2 parts of IJum and 5 parts of water, 20 parts of methyl methacrylate, 10 parts of ethyl methacrylate, 10 parts of t-butyl methacrylate, and 0.5 parts of γ-methacryloxyglobyltrimethoxysilane were injected over about 1 hour. The mixture was reacted and further aged for 1 hour. The product is then combined with a mixture of 30 parts of styrene, 10 parts of α-methylstyrene, 1 part of acrylonic acid and 0.5 parts of divinylbenzene, as well as a mixture of 0.2 parts of ammonium persulfate and 5 parts of water and 0.2 parts of sodium pyrosulfite. A mixture of 5 parts and 5 parts of water was injected over 2 hours each, reacted at 70°C, and aged for 1 hour. Next, the mixture was cooled, and 25% ammonia water was added to adjust the voice to obtain a resin emulsion. The obtained emulsion was designated as A-3, and its properties are shown in Table 1.

(A-4) Into the same reaction vessel as in A-2 above, add 100 parts of water and 7 parts of emulsifier (5 parts of Emulgen 120 and Hytenol N-08).
2 parts of potassium persulfate) and keep the internal temperature at 80℃.
．． 2 parts of acrylonitrile, 20 parts of styrene, 10 parts of butyl acrylate, and 5 parts of ethylene glycol dimethacrylate were injected over about 2 hours to react, and the mixture was further aged for 1 hour.

The resulting emulsion was then injected with 22 parts of styrene, 10 parts of α-methylstyrene, 10 parts of p-methylstyrene, 2 parts of methacrylic acid, and 1 part of divinylbenzene at 80°C.
After aging for 1 hour, the resin was cooled and pi (adjusted) to obtain a resin emulsion. The obtained emulsion was designated as A-4, and its properties are shown in Table 1.

(A-5) 100 parts of water and 6 parts of emulsifier in a reaction vessel as in A-2 above.
．． 5 parts (5 parts of Emulgen 120 and Hitenol N-0
A mixture of 0.2 parts of ammonium persulfate and 5 parts of water, a mixture of 0.2 parts of ammonium persulfate and 5 parts of water, and a mixture of 0.2 parts of ammonium persulfate and 5 parts of water. A mixture of 25 parts of methylnuccrylate, 25 parts of acrylonitrile, 1 part of acrylic acid, and 5 parts of ethylene glycol dimethacrylate was injected over 2 hours to react, and the mixture was further aged for 1 hour. The resulting emulsion was then mixed with 30 parts of styrene, p -) f Rustyrene IIL divinylbenzene 2
A mixture of 0.2 parts of ammonium persulfate and 5 parts of water and a mixture of 0.2 parts of sodium pyrosulfite and 5 parts of water were each introduced in 2 hours and reacted at 50°C.
After aging for 1 hour, it was cooled and pi (pi) was adjusted to obtain a resin emulsion. This emulsion was designated as A-6, and its properties are shown in Table 1.

(A-6 to π'0) In the above A-1 to A-5, emulsifier t-0,2 is added during the latter stage polymerization.
Resin emulsions were obtained in exactly the same manner as in Production pJA-1 to A-5, except that Repenol Wz (manufactured by Kao Soap Co., Ltd.) was added to the aqueous phase and reacted. The corresponding relationships are A-1 and A-6, A-2 and A-7, A-3 and A-8.
, A-4 and A-9, and A-5 and A-10. still,
Table 1 shows the properties of each emulsion.

(A'-1: Comparative production series) 100 parts of water and 5 parts of emulsifier (A-
1) (+- was added and stirred well. Next, the reaction vessel was heated and the internal temperature was maintained at 80°C, and 15 parts of 1-butyl methacrylate, 84 parts of p-methylstyrene, and 1 part of glycidyl methacrylate were added. The mixture and a mixture of 0.5 parts of ammonium persulfate and 5 parts of water were injected over about 2 hours, and the mixture was further aged for 1 hour.After that, it was cooled and subjected to p) IN conditioning to obtain a resin emulsion (A'-1). Table 1 shows the properties of this emulsion.

(A'-2: Comparative Production Example) A copolymer emulsion (1: za A copolymer emulsion (1) obtained by polymerizing 84 parts of p-methylstyrene and 0.5 parts of glycidyl methacrylate using the same amount of the emulsifier used in emulsion (1) was prepared with a solid content weight ratio of 21 near 9. The resin emulsion A'-2 was obtained by blending the resin emulsion A'-2.

(A'-3 to A'-6: Comparative production examples) The emulsifiers and monomers used in A-2, 3, 4, and 5 above were charged at once and homogeneously copolymerized for about 4 hours. Cool each resin emulsion (A'
-3 to 6) were obtained. The respective correspondences are A'-3 and A
-2, A'-4 and A-3, A'-5 and A-4 and A'
-6 and A-5, Chito (note) 1) Monomer composition: t-BA...L-butyl acrylate, GMA...glycidyl methacrylate, E
GDM...ethylene glycol dimethacrylate, p
-MSt...p~methylstyrene, filiMA...
・Ethyl methacrylate, α-MSt...α-methylstyrene, KBM-503...γ-methacryloxyglobyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), DVB...divinylbenzene 2) δ1: 1st 5olub1 of stage mo/-r-mixture
11 tyParameter (Solubility parameter) 3) δ! = Solubl of second monomer mixture
lltyParameter (Solubility parameter)
4) 1δ1-δ21: Difference in solubility parameters between the first and second stage mixtures 5) Glass transition temperature of the entire monomer composition (calculated value) Examples 1 to 3, Comparative rows 1 to 5 A-1 above and 16.1 parts of the resin emulsion of A-6, A'-1 and A'-2, and an acrylic-styrene copolymer resin emulsion (manufactured by Dainippon Ink and Chemicals Co., Ltd., VONCOAT EC) as a film-forming resin emulsion. −
880) 60.1 parts and 71 parts of rutile titanium dioxide
% aqueous dispersion as shown in Table 2, and slowly added 1.4 parts of tributyl phosphate, 16.5 parts of water, and 0.18 parts of hydroxyethyl cellulose to the mixture until the viscosity became constant. Stirred.

The resulting paints were applied side by side on a mores masking chart to form a film of the same thickness and air-dried for 3 days. Table 2 shows the physical and chemical test weight of these coatings.1) Particle diameter: Measured from a transmission electron micrograph of the emulsion.2) Mechanical stability: 50g of the emulsion was tested using a Marlon tester under a load of 10 kliil x 3,00 orpm. Measure the amount of aggregate formed after processing for minutes and calculate using the following formula.

(Evaluation)○...(A) is less than 0.1%△...
... (4) is 0.5% or more 3) Polymer solubility: The resin powder after water evaporation of the emulsion was added to each solvent and observed (concentration: 5%).

(Evaluation) ○...Does not dissolve ×...Dissolves 4) Light transmittance of paint film 2 After leaving the prepared paint for one day, apply it to a glass plate with a 3 mil applicator. , measured at 90° and 10° at 23°C and 65°RH.

5) Gloss (Glass plate): After the prepared paint was left for one day, it was applied to a glass plate using a 3 mil aggregator, and after drying for one day at 23°C and 65 mm RI, it was measured using a Murakami gloss meter.

6) Gloss (hidden main test paper) - After the prepared paint was left for one day, it was applied to the hidden test paper using a 6 mil applicator, and after drying for 5 days at 23°C and 65S RH, it was measured using a Murakami gloss meter. Measured.

7) Hiding rate: Measure the black and white areas of the test paper (manufactured by Japan Test Panel Industry Co., Ltd.) to hide the gloss of the coating film in 6) at 45° and 10°, and calculate the ratio using the formula below ( JIS K-5400).

45°10° diffuse reflectance of paint film on white ground 8) Water resistance:
After drying the glass plate coating film prepared in 4) for 1 day, it was immersed in water at room temperature for 14 days and visually observed (evaluation) ○...No swelling, 1 part of pristering present △... - Swelling, 〃 ×... Large swelling, measured with a glossy needle with a lot of pristalling, and expressed as a percentage of the gloss in 5).

Alkali resistance of 1: The glass plate coating film created in 5) was
After drying in the sun, it was immersed in a 2% NaOH, saturated Ca(OR)z aqueous solution for 14 days, and the condition of the coating film was visually judged.

(Evaluation) ○...Swelling, no blistering It is expressed as a percentage of gloss.

12) Washing resistance: Paint was applied to a matte PVC sheet using a 6 mil applicator, and after drying for 7 days, it was measured using a Gardner washing resistance tester.

(Evaluation) ○・・・No peeling of paint film after 2000 times △
・・・・・・Remove the coating film after 1000 to 2000 times ×
13) Weather resistance: The prepared paint was applied twice with a brush onto a slate board and dried for 7 days before being tested.

Visually judge the condition after 6 months of exposure.

(Evaluation) ○... Good △... Fair Evaluation) O... Good △... Fair and 16.1 parts of each emulsion A'-3 to A'-6 was added with an aqueous acrylic-styrene emulsion (manufactured by Dainippon Ink & Chemicals Co., Ltd., VON).
COAT 5460) and 16.58 parts of a 71% aqueous dispersion of rutile titanium dioxide were added.

1.4 parts of tributyl phosphate, 16.5 parts of water and 0.18 parts of hydroxyethylcellulose were added slowly and the mixture was stirred until its viscosity was constant. The above-mentioned various paints were applied side by side on a mores covert chart and a glass plate to form a coating film of the same thickness, and air-dried for 3 days. Table 3 shows the properties of the paint and the physical properties of the coating film. In addition, the solid content concentration of the paint is 46.1%, PVC
The capacity is 27.3 cm and the pwc is 39.4 cm.

Experiment 112, Comparative Reli 10 to 13 A-1 and commercially available resin emulsion, namely Rho
plex-OP-42 (acrylic-styrene copolymer resin emulsion, solid content 40.8%, Rohm & H
manufactured by AAS), 5plndrlft (polyester resin emulsion, solid content 29.6%, Encapsul
alr Inc), Lytoron2202 (styrenic resin emulsion, solid content 47.1%, mon
(manufactured by Santo) % Plastic Pigmen
t 722 (styrenic resin emulsion, solid content 49
．． 3%.

40 parts (solid content) of each (manufactured by Dow Cheml ca 1), 60 parts of water (solid content), 60 parts of acrylic-styrene emulsion (using M VONCOAT 5460, manufactured by Dainippon Ink and Chemicals Co., Ltd.), and 1. 4 parts of water, 165 parts of water and 0.18 parts of hydroxyethyl cellulose were added slowly and the mixture was stirred until its viscosity was constant.

The above-mentioned various paints were applied on a Morest concealer and on a gas plate, and air-dried for 3 days to form a coating of the same thickness. Figure 4 shows the properties of these emulsions and the physical properties of the coatings.

In addition, the solid content concentration of each paint is 43. (1, PVc 40.0
, PWC is 39.0%.

Examples 13 to 15 16.1 parts of the resin emulditane of A-1, epoxy ester water-soluble resin Waters as film-forming water-based resin
ol S-352 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Alkyd Dispersion VONCOAT CI)-5
20 (manufactured by Inu Nippon Ink Kagaku Kogyo Co., Ltd.) and Acrylic Disno R-shi! 30.0 parts each (solid content) of VONCOAT 7216 C (manufactured by Dainippon Ink and Chemicals) and a 71% aqueous dispersion of rutile titanium dioxide were blended as shown in Table 5, and tributyl phosphate was added to the mixture. 14 parts,
16.5 parts of water and 0.1 parts of hydroxyethyl cellulose
8 i-q of the mixture was slowly added and stirred until the viscosity became constant. The applied paint was placed on a mores masking chart to form a coating of the same thickness and air-dried for 3 days.

Table 5 shows the physicochemical properties of these coating films. Production Example B (Production method of (11) above) (B-1) Reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. 14 parts of t-butyl mecrylate,
Add a mixed solution of 82 parts of p-methylstyrene, 3 parts of acrylic acid, 1 part of glycidyl methacrylate, and 10 parts of Si478Q (Sorbitan Monoolea-1, manufactured by Kao Sekiken Co., Ltd.), and slowly add 50 parts of water to this. Room temperature, 80-11
Stirred at 00 rpm.

The obtained fc, W10 type emulsion was mixed with Repenol WZ
Mix with 50 parts of a 2.5% aqueous solution of (sodium alkylphenol ether sulfate, manufactured by Kao Seiken Co., Ltd.) and
The mixture was stirred at 350 rpm for about 5 minutes. (Inner water phase volume fraction φ storage in the first emulsification stage: 0.33, dispersed phase volume fraction φ in the second emulsification stage: 0.75) W10/W The composite emulsion is heated to 80°C Butyl 0 (t-butylpernexy 2-ethylhexanoate,
0.5 part (manufactured by NOF Corporation) was added and polymerized for 4 hours. Then, cool and add 0.1 part of 25% ammonia aqueous solution to adjust the pH.
Adjusted to 18.5.

The obtained emulsion had a solid content concentration of 51.8% and a viscosity of 2.
5eps (BM type rotational viscometer rotor A1, rotation speed 6
The average particle diameter measured with an electron microscope at pH 8.5 was 0.2 to 0.3 μm, and the average diameter of the microid in one particle was 0.05 to 0.1 μm. This non-film-forming resin emulsion is designated as B-1.

(B-2) 70 parts of styrene, t
- Pour a mixture of 20 parts of butyl acrylate, 8 parts of n-butyl acrylate, 2 parts of ethylene glycol dimethacrylate, and 5 parts of sorbitan sesquioleate, slowly add 40 parts of water, and leave at room temperature, 80-100 rp
The mixture was stirred at m. It was mixed with 60 parts of a 1.0% aqueous solution of the obtained Wlo fjM Emma Emulsion Mar 0 (sodium lauryl sulfate, manufactured by Kao Seiken Co., Ltd.) and heated at 250 to 350 r.
pm for about 5 minutes. (Inner water phase volume fraction φw/o' 0.30 in the first emulsification stage, dispersed phase volume fraction φw/w '0.69 in the second stage) The composite emulsion was heated to 80 ° C. Nosokmil H (cumene hydroperoxide, manufactured by NOF Corporation) 05
1 part was added and polymerized for 4 hours. Thereafter, the mixture was cooled and 0.5 part of aqueous 25-thiammonia solution was added to adjust the temperature to 8.5.

? The I Rare ft emulsion had a solid content concentration of 51%, a viscosity of 20 cps, and an average particle diameter of 0.2 to 03 μm measured using an electron microscope at pi (8,3). This non-film-forming resin emulsion was designated as B-2.

(B-3) In a reaction vessel similar to Production Example B-1, 30 parts of styrene, 20 parts of methyl methacrylate, 10 parts of α-methylstyrene,
10 parts of acrylonitrile, 10 parts of ethyl methacrylate, 10 parts of butyl methacrylate, 8 parts of n-butyl acrylate, 1 part of acrylic acid, 0.5 parts of divinylbenzene
part, r-methacryloxyglobyltrimethoxysilane 0
Add a mixture of 5 parts of polyoxyethylene (2) oleate and 7 parts of polyoxyethylene (2) oleate, slowly add 60 parts of water, and bring to a room temperature of 80%.
Stirred at ~1100 rpm. The obtained emulsion was mixed with Hitenol N-08 (alkylphenol ether sulfate ammonium salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5
% aqueous solution and at 250-350 rpm.
Stir for a minute. (Inner water phase volume fraction in the first emulsification stage φ cicada: 0.38, dispersed phase volume fraction in the second stage φw10/
w: 0.80) The composite emulsion is heated to 80°C, 0.5 part of ammonium persulfate is added, and polymerized for 4 hours. Thereafter, the mixture was cooled and the pH was adjusted to 88 by adding 3 parts of 25% aqueous ammonia.

The obtained emulsilon had a solid content concentration of 51.5% and a viscosity of 3.
The average particle size measured with an electron microscope at 1 cp@, voice 8.6 was 0.2 to 0.3 μm, and the average diameter of microdits in the particles was 0.05 to 01 μm. This non-film-forming resin emulsion is referred to as IB-3.

(B-4) Production [In a reaction vessel similar to IRJ B-3, 44 parts of styrene, 20 parts of acrylonitrile, 10 parts of α-methylstyrene, 10 parts of p-methylstyrene, 10 parts of butyl acrylate, 2 parts of methacrylic acid, A mixed solution of part S of ethylene glycol dimethacrylate, 2 parts of divinylbenzene, and 3 parts of glycerol monooleate was added, and 70 parts of water was slowly added thereto, followed by stirring at room temperature and 80 to 100 rpm. The obtained W10 type emulsion was mixed with Hitenol 07.
3 (yj? lyoxyethylene alkyl ether sulfate salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was mixed with 30 parts of a 5% aqueous solution and stirred at 250 to 350 rpm for about 5 minutes.

(Inner water phase volume fraction φW/' in the first emulsification stage: 0.4
3. Dispersed phase volume fraction φ in the second stage: 0.84)
W10/W The composite emulsion was heated to 80°C, 05 parts of potassium persulfate was added, and polymerized for 4 hours. After that, cool it down to 259
1+ Ammonia water was added to adjust - to 8.3.

The obtained emulsion had a solid content concentration of 50.3% and a viscosity of 2.
The particle size measured with an electron microscope at 0 cps, pi (:8.3) was 0.2 to 03 μm on average, and the average diameter of microdits in one particle was 0.05 to 0.1 μm.

(B-5) In a reaction vessel similar to Production Example B-1, 30 parts of styrene, 25 parts of methyl methacrylate, 259 parts of acrylonitrile, p-
Add 12 parts of methylstyrene, 5 parts of ethylene glycol dimethacrylate, 2 parts of divinylbenzene, 1 part of acrylic acid, and 6 parts of polyoxypropylene-polyoxyethylene cetyl alcohol, and add 50 parts of a 0.5-tidextrose aqueous solution. slowly at room temperature 80-100 rp.
Stir at m. Mix 4 fcW10 emulsion with 50 parts of emal 40 paste (higher alcohol sodium sulfate, manufactured by Kao Sekiken Co., Ltd.) and 50 parts of aqueous solution.
Stir for approximately 5 minutes at rpm. (Volume fraction of internal aqueous phase in the first emulsification stage φw10: 0.34-% Volume fraction of the dispersed phase in the second stage φw: 0.74) The composite emulsion was heated to 80°C and perbutyl 00.5 parts were added and polymerized for 4 hours. Thereafter, it was cooled and 25% ammonia water was added to adjust the voice to 8.8. The obtained emulsilon had a solid content concentration of 51.5%.

shi + L-+ to 1^1-11+++ contraction L"'FC2mA mountain LI-tlt-1 -, m-1r"w+-x-4-1 The average prognosis is 02-03μ? ? Micro in L1 particle? The average diameter of the id was 0.05 to 0.1 μm.

Examples 16-20 In Example 2, water-based coating compositions were obtained in the same manner as in Example 2, except that the non-film-forming resin emulsions were used in place of A-1 and B-1 to B-5. . Its physical properties are shown in Table 6. still,
The coating composition has a solid content concentration of 461%, PVC 27.3%,
The amounts of emulsions B-1 to B-5 were adjusted so that the pwc a was 9.4%.

Production Example C (Production method of (iii) above) (C-1) Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 50 parts of water and 5.0 parts of an emulsifier (for example, Kao Atlas Co., Ltd.) 3 parts of Emaldan 120i and 2 parts of Emal 20A) were added and stirred well. Next, the reaction vessel was heated, and the internal temperature was kept at 80°C, and a mixture of 14 parts of t-butyl methacrylate, 1 part of acrylic acid, 0.5 parts of glycidyl methacrylate, and 0 part of ammonium persulfate was added.
A mixture of 25 parts and 5 parts water was injected in about 1 hour, and an additional 1
Time aged. This emulsion is used as seed particles, 20 parts of toluene is added thereto to swell the seed particles, and then p-
After adding a mixture of 82 parts of methi, Rustyrene, 2 parts of acrylic acid, and 0.5 parts of glycitul methacrylate to further swell the seed particles, 00.5 parts of no-f-butyl was added, and 3 parts of Polymerized for hours. Thereafter, the mixture was cooled and a 25% ammonia aqueous solution was added to adjust the pH to 8.5.

The obtained emulsion had a solid content concentration of 44.8% and a viscosity of 4.
00 cps (B M type rotational viscometer rotor plate 3, rotation speed 6 Orpm, temperature 25°C), pHs, average particle diameter measured with an electron microscope at s is 0.4 to 0.5 μm
Average diameter of microdits in one particle 0.05-0.15
It was μm. This emulsion is designated as C-1.

Further, an emulsion obtained by distilling off toluene from C-1 under reduced pressure is designated as C-1'.

(C-2) 100 parts of water and emulsifier 78B as in Production Example C-1
(3 parts of Emuldan 920, 2 parts of Emuldan 120, and 2 parts of Hitenol N-08) were placed in a reaction vessel, heated to an internal temperature of 80°C, and dissolved with stirring. Next, while maintaining the internal temperature at 80°C, a mixture of 20 parts of t-butyl methacrylate and 1 part of ethylene glycol dimethacrylate, and a mixture of 25 parts of ammonium persulfate and 5 parts of water were injected over about 1.5 hours. It was further aged for 1 hour. This emulsion is made into seed particles and swelled by adding 20 parts of toluene, and then a mixture of 50 parts of styrene, 8 parts of n-butyl acrylate, and 1 part of ethylene glycol dimethacrylate is added to further swell the seed particles. After this, 0.5 parts of Perbutyl' was added and polymerized at 80°C for 3 hours. After that, cool it down for 25 minutes.
% ammonia water was added to adjust the total pH to 8.9.

The obtained emulsion had a solid content concentration of 45.5% and a viscosity of 1.
50 cps (B M rotational viscometer rotor A2, rotation speed 6 Orpm, temperature 25°C), the average particle diameter measured with an electron microscope at pH 8.2 is 0.4 to 0.5 μm.
Average diameter of microdits in one particle 0.05-0.15
It was μm. This emulsion is called '1ic-2.

Further, an emulsion obtained by distilling off toluene from C-2 under reduced pressure is referred to as C-2'.

(C-3) In the same manner as Production Example C-2, 100 parts of water and 7 parts of emulsifier (120 t-5.0 parts of Emuldan and Hytenol N-0
2 parts of 8) were placed in a reaction vessel, the internal temperature was raised to 80°C, and the mixture was stirred and dissolved. Next, the internal temperature was kept at 80°C, and a mixture of 20 parts of methyl methacrylate, 10 parts of ethyl methacrylate, 10 parts of t-butyl methacrylate, and 0.5 part of γ-methacryloxyglobytrimethoxysilane, 0.25 part of ammonium persulfate, and water was mixed. 5 parts of the mixture were injected over about 1 hour and an additional 1 h'l was added at t. 20 parts of toluene was added to this emulsion to swell it, and a mixture of 30 parts of styrene, 10 parts of α-metallic titanium, 10 parts of acrylonitrile, 8 parts of butyl acrylate, 1 part of acrylic acid, and 0.5 parts of divinylbenzene was added thereto. 00.5 parts of perbutyl after swollen seeds to a higher degree? Then, polymerization was carried out at 80°C for 3 hours. Thereafter, it was cooled and 25% ammonia water was added to adjust the temperature to 8.8.

The obtained emulsion had a solid content concentration of 45.4% and a viscosity of 1.
10 EP Zheng (BM type rotational viscosity needle rotor black 2, number of rotations 6 Orpm, temperature 25°C), pHs, average particle diameter measured with an electron microscope at s is 0.4 to 0.5 μm1
Average diameter of microdits in particles 0.05-0.15μ
It was m. This emulsion is designated as C-3. Also C
, -3 to which toluene was distilled off under reduced pressure.

1c-3'.

(C-4) Similarly to Production Example c-2, 100 parts of water and 7 parts of emulsifier (
Emaldan 120'Jk5 part and Hitenor N-08'
(r2 parts) was placed in a reaction vessel, the internal temperature was raised to 80°C, and the mixture was stirred and dissolved. Next, the internal temperature was kept at 80°C, and a mixture of 20 parts of acrylonitrile, 20 parts of styrene, 10 parts of butyl acrylate, 5 parts of ethylene glycol dimethacrylate, and a mixture of 0.25 parts of ammonium persulfate and 5 parts of water were injected over about 2 hours. , and further aged for 1 hour. This emulsion was made into seed particles and swollen by adding 20 parts of toluene, 22 parts of polystyrene, 10 parts of α-methylstyrene,
After adding a mixture of 10 parts of p-methylstyrene, 2 parts of methacrylic acid, and 1 part of divinylbenzene to further swell the seed particles, 00.5 parts of perbutyl was added, and the mixture was heated at 80°C for 30 minutes.
Polymerized for hours. Thereafter, it was cooled and 25% ammonia water was added to adjust the pl (i) to 8.9.

The obtained emulsion had a solid content concentration of 45.0% and a viscosity of 1.
20 cps (BM type rotational viscometer rotor flat 2, rotation speed 6
The average particle diameter measured with an electron microscope at pH 8 and 9 was 0.4 to 0.5 μm, and the average diameter of microvoids in one particle was 0.05 to 0.15 μm. This emulsion is called '1c-4. Also C-4
Emarzo is obtained by distilling toluene off under reduced pressure.

Let C-4' be the key.

(C-5) 100 parts of water and emulsifier 6, 5 as in Production Example C-2
Part (with 5 parts of Emaldan 120'e) -Itenol N-
08
The mixture was heated and stirred to dissolve. Next, keep the internal temperature at 50℃ and add 0.2 parts of ammonium persulfate and 0.2 parts of sodium pyrosulfite.
5 parts each of water and 2 parts of methyl methacrylate
A mixture of 5 parts of acrylonitrile, 25 parts of acrylonitrile, 1 part of acrylic, and 5 parts of ethylene glycol dimethacrylate was injected over a total of 2 hours, and further aged for 1 hour. This emulsion was used as seed particles, and then 20 ml of toluene was added to swell the seed particles, and a mixture of 30 parts of styrene, 12 parts of p-methylstyrene, and 2 parts of divinylbenzene was added to further refine the seed particles. Perbutyl 0'k after swelling with
5 parts of O was added, the temperature was raised to 80°C, and polymerization was carried out at 80°C for 3 hours, after which it was cooled and 25% aqueous ammonia was added to adjust the pH to 8.8 in total.

The obtained emulsion had a solid content concentration of 4'4.0%,
Viscosity 80 cps (B M type rotational viscometer rotor shop 2
, rotation speed 6 Orpm, temperature 25°C), Pn 8.
s-c! Average particle diameter measured using an electron microscope: 0.4-0.
5μm, average diameter of microvoids in particles 0.05~0
．． It was 15 μm. This emulsion is called 'zC-5. Further, the emulsion obtained by completely removing toluene from C-5 under reduced pressure is designated as C-5'.

(C-, 6) Same as Production Example C-5, 100 parts of water and 6.5 parts of emulsifier.
(Emuldan 120'i 5 parts and Hitenol N-0
8't (1.5 parts) was placed in a reaction vessel, the internal temperature was maintained at 50°C, and the mixture was thoroughly stirred. Next, while keeping the internal temperature at 50°C, a mixture of 0.2 parts of ammonium persulfate, 0.2 parts of sodium pyrosulfite, and 5 parts of water each, 10 parts of methylstyrene, 12 parts of p-methylstyrene, 5 parts of ethylene glycol dimethacrylate, A mixture of 2 parts of divinylbenzene and 20 parts of toluene was injected over 3 hours, and the mixture was further aged for 1 hour. Thereafter, it was cooled and 25% aqueous ammonia was added to adjust the pH'i to 8.5.

The obtained emulsion had a solid content concentration of 44.3% and a viscosity of 9.
50 cps (value of BMm rotational viscometer C' I A4, rotation speed 5Qrpm, temperature 25℃), p) N at 18.5
Average particle size measured using a microscope: 0.05-0.1 μm
, average diameter of microvoids in particles 001-0.03μ
It was m. This emulsion is all c-6. In addition, toluene from C-6 was distilled off under reduced pressure, and the margin was removed from C-6.
'.

Examples 21 to 26 In Example 2, non-film-forming resin emulsion 'zA-
A water-based coating composition was obtained in the same manner as in Example 2 except that C-1' to C-6' were used in place of C-1. Its physical properties are shown in Table 7.

C-1 to be 27.3%, pwc 39.4%
The amount of emulsion from ' to 6' was adjusted.

Example 27 No. 111 C-1 (all benzene is included in the core)
A coating composition was obtained with the same formulation as in Example 12 using a vacuum cleaner. Its physical properties are shown in Table 8. Also, for comparison, Comparative Example 10~
13 is also shown in Table 8.

Said Example 2. The compositions of i6 and 21, Comparative Examples 3 and 5 were applied to a glass plate and kept at room temperature for - weeks, then 50
After drying at ℃ for 24 hours, it was frozen by immersing it in liquid nitrogen, and then the broken cross section was observed with a scanning electron microscope, and each cross section was shown as a photograph (magnification: xsooox%) as 1 to 5. Ta. The hollow-looking particles in Figures 1 to 3 (Examples 2, 16, and 21) are non-film-forming vinyl resin particles.

[Brief explanation of drawings]

Figures 1 to 5 are Example 2, Example 16, and Example 2, respectively.
1. Each coating film obtained from each composition of Comparative Example 3 and Comparative Example 5 was immersed in liquid nitrogen and is an electron micrograph showing the cross-sectional state of the coating film observed with a cross-sectional full-scanning electron microscope after freezing. . Figure-1: Example 2 #2: #16 #3: #21 14: Comparative Example 3 #5: #5 Figure-1 Figure-2 Figure-3 Figure-Material Map-S Procedure Correction W (Voluntary ) ■, Small case indication 1982 Patent Application No. 79559 2, Name of invention Water-based paint composition 3, ? Relationship with the case of a person who commits illegal acts Patent applicant: 3-35-58-Sakashita, Itabashi-ku, Tokyo 174 (2)
88) Kawamura, Representative of Dainippon Ink and Chemicals Co., Ltd.
Kuni Shigeru 4, Agent: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone number: Tokyo (03) 272-4511 (main representative) 6
, Contents of correction: ``It will be difficult.Also, the resin emulsion is obtained using polymerizable vinyl monomers, but usually α, β-
The ethylenic non-saturated carboxylic acid is obtained by using its salt in an amount of less than 5 M%, preferably 4.5% by weight or less, more preferably 3.5% by weight or less based on the total amount of monomers. If the amount of α, β, β-ethylene saturated carboxylic acid or its salt exceeds 5% by weight, the physical properties of the paint film, especially alkali resistance, water resistance, and weather resistance, will deteriorate even when paint additives such as titanium oxide are used together. This results in a coating composition with reduced properties. Correct to J. (2) Delete "Also" in the 4th line of page 4 of the same book. (Hereinafter referred to as 2) Patent Application No. 79559, dated August 1989, 2 Name of the invention: Water-based paint composition 6, Relationship with the person making the amendment Case Patent applicant: 3-chome Sakashita, Itabashi-ku, Tokyo, 174 65 No. 58 (288
) Shigeru Kawamura, Representative of Inu Nippon Ink Chemical Industry Co., Ltd.
Country 4, Agent Address: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 106 & Contents of amendment (1) “It will be difficult. Resin emulsions are obtained using polymerizable vinyl monomers, and are usually α-, β-
It is obtained by using an ethylenically unsaturated carboxylic acid or a salt thereof in an amount of less than 5% by weight, preferably 4.5% by weight or less, and more preferably 6.5% by weight or less based on the total amount of monomers. If the amount of α,β-ethylenically unsaturated carboxylic acid or its salt exceeds 5% by weight, the physical properties of the paint film, especially alkali resistance, water resistance, and weather resistance, will deteriorate even when paint additives such as titanium oxide are used together. This results in a coating composition with reduced properties. However, the resin emulsion is obtained using polymerizable vinyl monomers, but usually α, β-
It is obtained by using ethylenically unsaturated carboxylic acid or its salt in an amount of less than 5% by weight, preferably 4.5% by weight or less, more preferably 5.5% by weight or less based on the total amount of monomers. When such a resin emulsion is obtained by further polymerizing a polymerizable vinyl monomer on a seed particle polymer (core polymer) obtained by polymerizing a polymerizable vinyl monomer, a nuclide particle polymer is used. Of the monomers constituting it, the amount of α,β-ethylenically unsaturated carboxylic acid or its salt is less than 5% by weight, preferably 4.5% by weight or less, and more preferably 35% by weight or less. is suitable. If the amount of α,β-ethylenically unsaturated carboxylic acid or its salt exceeds 5% by weight, the physical properties of the paint film, especially alkali resistance, water resistance, and weather resistance, will deteriorate even when paint additives such as titanium oxide are used together. This results in a coating composition with reduced properties. ” is corrected. (2) From page 13, line 2 from the bottom to page 14, line 4 of the same book, ``0 to 90 parts by weight are used as seed particles...
Emulsion polymerization after concave swelling is changed to 0 to 90 parts by weight, preferably 1 to 50 parts by weight of (seed particles) and 0.1 to 100 parts by weight of a water-insoluble non-polymerizable solvent. When used, after swelling in the solvent, add 99 to 10 parts by weight of a polymerizable vinyl monomer (W) and 1 to 50 parts by weight of a polyfunctional crosslinking monomer (G), including one type of particles. (3) "14 parts of t-butyl methacrylate, 1 part of acrylic acid" on page 26, lines 7-8 of the same book.
4.5 parts of t-butyl methacrylate H, 0 parts of acrylic acid
．． Corrected to ``Part 5''. (4) Table 1 on page 60 of the same book is corrected as follows. 1H Continuation NeliIi Original (self-proposal) October q, 1980 Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case 1980 Patent Application No. 79559 2. Name of the invention 3. Five things that make supplement + E (relationship with 1) Patent applicant: 35-58, Sakashita 3-1, Itabashi-ku, Tokyo 174 (2)
88) Inu Nippon Ink Chemical Industry Co., Ltd. 71 Ishi Table 1r Kawa I.J Shigeru Tsuki I 4, Agent 〒103 Chuo-ku, Tokyo 11 Honbashi 3] Item 7 No. 20 Inu I
Ihon Ink Kagaku Jogyo Co., Ltd. Phone: Tokyo (03) 272-4511 (Dog I(',
Table) 6, Supplementary IF contents (+l lid, page 13, line 2 from the bottom to page 14, line 4
row (correction point on 8JNS day, 1981) r (8 particles) 0-90 city weight part
−−−−−−−−−−−−−−−−−−−−−−−−−
``Emulsion polymerization'' is replaced by ``(seed particles) 0 to 90 parts by weight, preferably 1 to 50 parts by weight and 0.1 part of a non-polymerizable solvent insoluble in water.
~100 parts by weight, when seed particles are used, after swelling in the solvent, 99 to 10 parts by weight of polymerizable vinyl monomer (F) and 0.1 to 50 parts by weight of polyfunctional crosslinkable monomer CG) If part by weight is added and seed particles are included, it will swell to a higher degree and undergo emulsion polymerization.''(that's all)

Claims (1)

[Scope of Claims] 1. An aqueous coating composition comprising a non-film-forming vinyl resin emulsion (1) in which resin particles have a core shape and a film-forming aqueous resin (If). 2. The solid content weight ratio of the non-film-forming vinyl resin emulsion (1) and the film-forming aqueous resin (II) is (1): (I
I)=1:100-100:1 The composition according to claim 1 @ item 1◎ 3. The resin particles of the non-film-forming vinyl resin emulsion (1) are hollow, or The composition according to claim 1, characterized in that the core contains a solvent.