JPS6172003A - Production of resin emulsion and pulverization - Google Patents

Abstract

PURPOSE:An emulsion is obtained using a polymerizable vinyl monomer, a lipophilic emulsifier, hydrophilic a emulsifier, and water and the monomer is polymerized to produce a not-film-forming emulsion which gives coating films with high opacifying power, good luster and high weather resistance, when it is added to a coating. CONSTITUTION:A polymerizable vinyl monomer such as methyl (meth) acrylate or hexyl vinyl ether, a lipophilic emulsifier of less than 13 HLB, e.g., sorbitol monooleate, a hydrophilic emulsifier of more than 13 HLB, e.g., alkali alkylbenzene-fulfonate and water are used to prepare a W/O/W type complex emulsion, then the monomer is polymerized to give a resin emulsion with fine pores inside. The emulsifiers are preferably used in a proportion of 1-30wt.% of lipophilic and less than 5% of hydrophilic one based on the vinyl monomer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a non-film-forming resin emulsion having small pores inside that is useful for paints; various coating agents for paper, textiles, leather, etc.; various additives, etc. This invention relates to a method for producing and powdering the same.

[Conventional technology]

In recent years, methods for producing non-film-forming bead-shaped resin particles having small pores have been proposed. For example, polyester-based products are patented in Australia! It is described in the specification of No. 455277 and the like. That is, an aqueous pigment dispersion is suspended in droplets in an unsaturated polyester solution containing an unsaturated monomer such as styrene, the resulting suspension is dispersed in water in the form of beads, and then polymerized. Furthermore, a non-film-forming resin emulsion having small pores inside which is stabilized by adding a water-soluble polymer such as partially hydrolyzed polyvinyl acetate, or an unsaturated polyester resin having a polyethylene oxide chain is used; An improved version of the above emulsion without the addition of polymers (JP-A-51-12948
(see Specification No. 5) has been proposed. However, although these coating compositions using non-film-forming resin emulsions have excellent hiding properties, they have the disadvantage that they result in coating films with no visible gloss at all.

Also, a vinyl-based 1m layer is disclosed in US Patent No. 31522.
It is proposed in specification No. 80. That is, when producing a non-film-forming vinyl resin emulsion having small pores, α,β-ethylenically unsaturated caldicic acid or salts thereof are copolymerized as a monomer of at least 5 weight or more as core particles. and then adding at least one monoethylenically unsaturated sheath monomer to form a sheath polymer on the core granules and, after polymerization, neutralizing and swelling the core polymer with an aqueous volatile base. This is a method for producing a non-film-forming emulgene having small pores.

Coating compositions using such aqueous volatile base neutralized swelling non-film-forming resin emulsions have hiding properties, but have poor gloss and have drawbacks, particularly in terms of durability such as weather resistance and alkali resistance.

In addition, a method for producing a non-film-forming resin emulsion having small pores without using a carboxylic acid monomer as described above (J
, Polym, Sal , +Polym, Lett,
Edn, .

19, 143 (1981)) has also been proposed.

That is, styrene is emulsion polymerized on core particles of an emulsion bottle of polymethyl methacrylate to form a core polymer. In this case, a non-film-forming resin emulsion with a core-sheath weight ratio of 1:2 and a non-volatile content of 15 g was obtained, the structure of which was indirectly observed by electron micrographs.

However, such a non-film-forming resin emulsion having small pores with a low solid content does not react sufficiently, so it is of little practical use from the viewpoint of miscibility and mechanical stability during paint formulation.

[Problem that the invention seeks to solve]

The present invention is directed to a non-film-forming oar fat emulsion or a powdered product thereof that, when used in a paint, provides a coating film that has excellent hiding properties and also satisfies physical properties such as gloss, weather resistance, and alkali resistance. The purpose is to provide a manufacturing method for Furthermore, the present invention is also a method for producing emulsions or powdered products thereof, which can be applied not only to paints but also to other uses.

[Means for solving problems]

The present inventors have conducted intensive studies on a method for producing a core-shaped non-film-forming vinyl resin emulsion with small pores that has excellent physical properties as described above and is highly practical, and a method for powdering the same. It's arrived.

That is, from a polymerizable vinyl monomer, a lipophilic emulsifier, a hydrophilic emulsifier, and water to water-oil-one-water (W10/W)
A method for producing a non-film-forming vinyl resin emulsion having small pores inside, which comprises obtaining an m-composite emulsion and then polymerizing a polymerizable vinyl monomer, and the non-film-forming vinyl resin emulsion. , provides a powdering method.

The polymerizable vinyl monomer used in the present invention is one having one polymerizable vinyl group in the molecule (6t), such as evamethyl-, ethyl-, clopyl-1n-butyl-1l-butyl-1t-butyl. (meth)acrylic acid esters such as -1n-amyl-11-amyl-, hexyl-, octyl-, nonyl-1f-yl-, dodecyl-, octadecyl-, cyclohexyl-, phenyl- or habenzyl (meth)acrylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butylade or "vinyl persate"; vinyl ethers such as methyl, ethyl, clopyru, butyl, amyl or hahexyl vinyl ether; such as acrylonitrile. Vinyl cyanides; vinyl heronates such as vinyl chloride or vinylidene chloride; or dialkyl esters of unsaturated dibasic acids such as dialkyl esters of maleic acid, fumaric acid, or itaconic acid, such as styrene modi or vinyltoluene. Olefins; monoenes and dienes such as ethylene and butadiene, unsaturated acids such as α,β-ethylenically unsaturated cargonic acid, vinylsulfonic acid or styrenesulfonic acid, or salts thereof;
Glycidyl compounds such as (methyl)glycidyl (meth)acrylate; (meth)acrylamide or their N-methylolated products or alkoxylated products thereof; α,β-ethylenically unsaturated containing silane groups such as vinyltrichlorosilane or vinyltriethoxysilane monomer;
Alternatively, there are hydroxyl group-containing α, β-ethylenically unsaturated monomers such as β-hydroxyethyl (methacrylate), which can be used alone or in combination of two or more.

In addition, the polymerizable vinyl monomer used in the present invention is α, β
-Ethylenically unsaturated Cal? A non-film-forming resin with improved water resistance and alkali resistance can be obtained by containing less than ios of each monomer weight, preferably less than 8 g, and more preferably 6 g, of phosphoric acid or its salt. This is suitable because it can bring about

Since the above-mentioned polymerizable vinyl monomer improves the solvent resistance of the resulting resin, it is preferable to use a polyfunctional crosslinkable monomer together. The amount of polyfunctional crosslinking monomer used is 1 total monomer amount.
0 to 50 parts by weight, particularly preferably 0 to 30 parts by weight. Similarly, if the amount exceeds 50 parts by weight, it is not preferable because it becomes difficult to produce an emulsion.

Examples of polyfunctional crosslinkable monomers include those having two or more polymerizable unsaturated bonds in the molecule, such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-7' ethylene glycol dimethacrylate. Examples include methacrylate, propylene glycol somethacrylate, divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol diacrylate), and 1,3-butylene glycol soacrylate.

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

Examples of hydrophilic emulsifiers include commercially available anionic emulsifiers such as alkylbenzene sulfo/acid alkali salts, alkyl sulfate alkali salts, alkyl sulfate alkali salts, polyoxyethylene alkylphenol sulfate alkali salts, and nonions with a high HLB, preferably 13 or more. Examples include substances having surfactant ability such as type emulsifiers, cationic emulsifiers, other reactive emulsifiers, and acrylic oligomers, and these can be used alone or in combination of two or more. Among these, anionic emulsifiers and nonionic emulsifiers are stable water/oil/water (W10/W)! This is preferred because it forms a composite emulsion.

The amount of such a lipophilic emulsifier used is generally 1 or more, preferably 1 or more, based on the weight of the polymerizable vinyl monomer.

The amount of hydrophilic emulsifier used is generally 10% or less, preferably 5% of the weight of the polymerizable vinyl monomer.
In the following, the weight ratio of lipophilic emulsifier/hydrophilic emulsifier is determined to be 0.1 or more, preferably 0.5 or more, and more preferably 0.7 to 10.

In the present invention, protective colloids often used in emulsion polymerization can also be used. Examples of protective colloids include water-soluble polymeric substances such as polyvinyl alcohol and hydroxyethyl cellulose. When these protective colloids are used in emulsion polymerization, the resulting emulsions have a large particle size and good hiding properties. , the weather resistance decreases, so when used, the amount should be 5% by weight or less, preferably 2% by weight or less based on the total weight of the monomers. O Water/Oil/Water (W10/W) in the present invention A dispersed composite emulsion is one in which droplets of a polymerizable vinyl monomer containing water by a lipophilic emulsifier are uniformly dispersed in water by a hydrophilic emulsifier. Such an emulsion can be made by, for example, stirring a polymerizable vinyl monomer, a lipophilic emulsifier, and water to prepare a stable water-in-oil (WO 凰) emulsion, which is then mixed with water containing a hydrophilic emulsifier. It can be easily obtained by dispersing it in

The WLO emulsion is produced by stirring the above-mentioned raw materials at a rotational speed of usually 50 to 11,000 rpm.

The total amount of water in the droplets of polymerizable vinyl monomer in the W10/Wfi composite emulsion is 0.1 to 0.1% of the polymerizable vinyl monomer.
100% by weight, preferably 1 to 80% by weight. or,
The (inner water phase) volume fraction is preferably 0.10 to 0.9
5, preferably 0.3 to 0.9. Such volume fraction is the volume of water divided by the volume of polymerizable vinyl monomer.

When the monomers in the W10/Win emulsion are subjected to ordinary emulsion polymerization, a solvent is used to carry out emulsion polymerization to produce a non-film-forming vinyl resin at room temperature that has concealing properties and has an internal aqueous phase within the particles. This can be done by producing an emulsion. Such a catalyst is preferably added to the W10/W composite emulsion, and in this case, an oil-soluble catalyst is preferred. Any catalyst that is commonly used in emulsion polymerization may be used; typical examples include water-soluble inorganic peroxides or persulfates such as hydrogen peroxide and ammonium persulfate; Organic peroxides such as gas oxide and benzoyl peroxide; chiazo compounds such as azobisisobutyronitrile, etc.
These may be used alone or as a mixture of two or more. The amount used is about 0.1 to 2 inches based on the total weight of the monomers. It goes without saying that a method generally known as a redox polymerization method using a combination of these catalysts, metal ions, and a reducing agent may also be used.

Polymerization of the monomers in the combined emulsion is generally carried out at 0 to 100°C, preferably at 3°C in the presence of a catalyst.
It is carried out at a temperature of 0 to 90°C.

The non-film-forming vinyl resin emulsion thus obtained can be distilled off under reduced pressure to optionally remove the contained solvent to obtain a resin emulsion having small pores (micromade) inside. At this time, the solvent was distilled off under reduced pressure at 20 to 3
It is usually carried out under conditions of reduced pressure of about 0-Hg and heating of about 60°C. The non-film-forming vinyl resin particles produced usually have a particle size of 0.1 to 5.0 microns, preferably 0.2 to 1.0 microns.
It has a particle size of 0 microns, and the small pores (micro pores) inside it are usually 0.01 to 1.0 microns.
Preferably, it has a diameter of 0.02 to 0.5 microns.

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

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 a transmission type electron microscope or a scanning electron microscope, and small pores can also be easily confirmed in a coating film after compounding the paint. In addition, it is also possible to measure the specific gravity of the emulsion.

In the present invention, the non-film-forming vinyl resin emulsion described above can be powdered by drying. Powderization can be carried out by any commonly used emulsion powderization method, such as spray drying at a temperature of 135 to 155°C, tray drying (in a hot air atmosphere) at a temperature of 50 to 70°C, or fluidized bed drying. be able to. The solid content concentration of the emulsion upon drying is preferably about 30 to 60% by weight.

The particle size of the obtained non-film-forming vinyl resin powder is almost the same as the particle size of the emulsion used. Such a powder can be redispersed in water by adding a dispersant such as an emulsifier or a protective colloid if necessary. Powders have excellent hiding properties, and can produce coatings with excellent physical properties such as gloss, water resistance, alkali resistance, weather resistance, etc. when added to paints, for example.In particular, titanium oxide, which is commonly added to paints, When added in small amounts, the hiding property is further increased and a coating film with high gloss retention is produced.

Such emulsions and powders can be added to various things other than paints, such as paper coating inks, adhesives, pressure-sensitive adhesives, leather sealants, brimer agents, and abrasion resistance improvers for textiles. Further, the powder is mixed with a molding resin such as polyvinyl chloride, polyester, polystyrene τ polyethylene, polypropylene, etc., and molded into miscellaneous goods, toys, industrial parts, electrical parts, etc. In addition, when applied to paper and cloth, it produces artificial leather, rugs, clothing, waterproof sheets, etc., and when applied to metal plates, it produces corrosion-resistant metal plates (pre-coated metal).
When you bring about -, you get -.

〔Example〕

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.

Example 1 52 parts of styrene, 10 parts of α-methylstyrene, 20 parts of acrylonitrile, 10 parts of n-butyl acrylate, 2 parts of methacrylic acid, and ethylene were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer. Add a mixed solution of 5 parts of glycol dimethacrylate, 1 part of divinylbenzene, and 10 parts of Sulfon 80 (sorbitan monooleate, Kao Seiken Co., Ltd. fi), slowly add 50 parts of water, and let it cool at room temperature for 80 minutes. Stirred at 10 Orpm. The obtained fcW10N emulsion was mixed with 50 parts of a 2.5% aqueous solution of Repenol WZ (sodium furkylphenol ether sulfate, manufactured by Kao Seiken Co., Ltd.) to give a concentration of 250 to 350%.
Stir for approximately 5 minutes at rpm. (Internal aqueous phase volume fraction φw/. in the first emulsification stage: 0.33, dispersed phase volume fraction φw7o7w in the second emulsification stage: O-75) The composite emulsion was heated to 80°C, / 4-Butyl 0 (t-butylpernexy 2-ethylhexanoate, manufactured by NOF Corporation)
0.5 part was added and polymerized for 4 hours. Then cool down to 25%
- was adjusted to 8.8 by adding 0.1 part of ammonia aqueous solution - The obtained emulsion had a solid content concentration of 51.0% and a viscosity of 20 cps (BM type rotational viscometer rotor 41, rotation speed 6 Orpm, temperature 25 ° C. The average particle diameter measured using an electron microscope at pH 8.8 was 0.4 μm, and the diameter of microvoids in one particle was 0.10 to 0.15 μm. This non-film-forming, fat-resistant emulsion was designated as A-1.

Example 2 In a reaction vessel similar to Example 1, 30 parts of styrene, 22 parts of p-methylstyrene, 20 parts of methyl methacrylate, 20 parts of acrylonitrile, 1 part of acrylic acid, 5 parts of ethylene glycol dimethacrylate, and 2 parts of divinylbenzene were added. and 5 parts of sorbitan sesquioleate, slowly added 40 parts of water, and heated at room temperature, 80-100 rp.
The mixture was stirred at m.

The obtained W10fi emulsion was mixed with 60 parts of a 1.0% aqueous solution of Emal O (sodium lauryl sulfate, manufactured by Kao Seiken Co., Ltd.) and stirred at 250 to 350 rpm for about 5 minutes. (Inner water phase volume fraction φ at the first emulsification stage: 0.
30. Volume of dispersed phase in the second stage W/.

Fraction φw10/w' 0-69) The composite emulsion was heated to 80°C and perc mill H
(cumene hydroperoxide, manufactured by NOF Corporation) 0.5
1 part was added and polymerized for 4 hours. Thereafter, the mixture was cooled and 5 parts of 25% aqueous ammonia MO was added to adjust the temperature to 8.5.

The resulting emulsion had a solid content concentration of 52% and a viscosity of 25%.
cps, the average particle diameter measured with an electron microscope at pH 8.4 is 0.3 μm.The average diameter of microvoids in one particle is 0.
．． It was 05-0°1 μm. This non-film-forming resin emulsion is designated as A-2.

Example 3 Reaction vessel Kt-butyl acrylate 1 similar to Example 1
0 parts, 20 parts of methyl methacrylate, 55 parts of styrene,
A mixture of 10 parts of n-butyl acrylate, 5 parts of ethylene glycol dimethacrylate, and 7 parts of tophoryoxyethylene (2) oleate was added thereto, 60 parts of water was slowly added thereto, and the mixture was heated to a room temperature of 80 to 1°C.

Stirred at rpm. The obtained Wlo fi emulsion was mixed with 40 parts of Hytenol N-08 (alkylphenol ether sulfate ammonium salt, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) in a 5% aqueous solution, and the
Stir for a minute. (Inner water phase volume fraction φw at the first emulsification stage
10:0.38, dispersed phase volume fraction φw10 in the second stage
7w' 0-80) The composite emulsion was heated to 80°C.
0.5 part of ammonium persulfate was added and polymerized for 4 hours. Thereafter, the mixture was cooled, and 3 parts of ammonia water was added to adjust the pH to 18.7.

The obtained emulsion had a solid content concentration of 51% and a viscosity of 21%.
The average particle diameter measured with an electron microscope at ape% pH 8.7 is 0.3μ, and the average diameter of microdites in the particles is 0.0.
It was 5 to 0.1 μm. This non-film-forming lipophilic emulsion,
Let's say A-3.

Example 4 In a reaction vessel similar to Example 1, 30 parts of styrene, 10 parts of ethyl methacrylate, 25 parts of α-methylstyrene, n-
12 parts of butyl acrylate, 2 parts of acrylic acid, γ-methacryloxyglobyltrimethoxysilane (KBM-50
3. Shin-Etsu Chemical Co., Ltd.) 0.5 parts 1 divinylbenzene 0
．． Add a mixture of 5 parts toglycerol monooleate and 3 parts, and slowly add 70 parts of water to the mixture and bring to room temperature, 80-10
Stirred at 0 rpm. The obtained Wlo emulsion was mixed with Hitenol 073 (polyoxyethylene alkyl ether sulfate soda salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5
The mixture was mixed with 30 parts of an aqueous solution of water and stirred at 250 to 350 rpm for about 5 minutes. (Volume fraction of internal aqueous phase φ at the first emulsification stage
: 0.43, dispersed phase volume φ in the second stage fraction φw10//W: 0.84) The composite emulsion was heated to 80° C., 0.5 part of potassium persulfate was added, and polymerization was carried out for 4 hours. After that, cool it down for 25 minutes.
Aqueous thiammonia was added to adjust the temperature to 8.5.

The obtained emulsion had a solid content concentration of 50% and a viscosity of 31
cps, pH: 8.5, the particle diameter measured using an electron microscope was an average of 0.3 μm, and the average diameter of microvoids in one particle was 0.05 to 0.1 μm.

This non-film-forming resin emulsion was designated as A-4.

Example 5 30 parts of styrene, 5 parts of methyl methacrylate, 10 parts of t-butyl methacrylate, p
- 52 parts of methylstyrene, 0 glycidyl methacrylate
．． Add 5 parts of divinylbenzene, 0.5 parts of divinylbenzene, and 6 parts of polyoxypropylene-polyoxyethylene cetyl alcohol, slowly add 50 parts of water, and bring to a room temperature of 80-10
Stirred at 0 rpm. The resulting W10 emulsion was mixed with emulsion 40 paste (higher alcohol sodium sulfate).

(manufactured by Kao Sekiken Co., Ltd.) 5. Mix with 50 parts of an aqueous solution of 250-3
Stir at 50 rpm for about 5 minutes. (Inner water phase volume fraction φy10 in the first emulsification stage: O-34, dispersed phase volume fraction φVo//w in the second stage: 0.74) The composite emulsion was heated to 80°C, and perbutyl O 0.5 part of was added and polymerized for 4 hours. Thereafter, it was cooled and 25% of ammonia water was added to adjust the - to 8.8. Obtained emal zo,
The solids concentration is 52 inches, the viscosity is 28 cps, and the pi(8
, 1, the average particle size measured using an electron microscope was 0.3 μm.
Average diameter of microdits in one particle 0.05-0.1μ
It was m.

This non-film-forming emulsion is referred to as A-5. Comparative Example 1 Into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 100 parts of water and 5 parts of emulsifier (Emul 3 parts of Emar/120 and 2 parts of Emal 20A) were added and stirred well. Next, the reaction vessel was heated, the internal temperature was kept at 80°C, and the monomer mixture used in Example 1, 0.5 part of ammonium persulfate, and 5 parts of water were mixed.
The mixture was injected in about 2 hours and aged for an additional hour.

After that, the resin emulsion (B-
1) was obtained. Table 1 shows the properties of this emulsion.

Comparative Examples 2 to 5 The monomer mixtures used in Examples 2 to 5 and the emulsifier used in Comparative Example 1 were charged at once and subjected to homogeneous copolymerization, mixed for 4 hours, and then cooled to form each resin emulsion B. -2~5
I got it. These emulsions.

The particles did not contain microditons. Moreover, these properties are shown in Table 1.

Comparative Example 6 In a reaction vessel similar to Example 1, 10 parts of emulsifier (Example 1
) and 15 parts of t-butyl methacrylate, p-
74 parts of methylstyrene, 10 parts of acrylic acid. A mixed solution of 1 part of glycidyl methacrylate was added, and 50 parts of water and Yuri were added thereto, followed by stirring at room temperature and 80 to 1100 rpm.

The subsequent operations were exactly the same as in Example 1, and Emarzo,
Sample B-6 was prepared.

Table 1 shows the properties of this non-film-forming fat-reducing emulsion.

(Note) 1) Monomer composition: AA--acrylic acid, n-BA-
... Re-butyl acrylate 1, N... Acrylonitrile, St... Styrene, MMA... Methyl methacrylate, t-BA... t-Fotsu c7. acrylate, G
MA...glycidyl methacrylate, EGDM...
Ethylene glycol dimethacrylate, p-MSt・
...p-methylstyrene, IEMA...ethyl methacrylate, α-MSt...α-methylstyrene, KB
M-503...r-Methacryloxypropyltrimethoxysilane<Shin-Etsu Chemical Co., Ltd.), DvB...Divinylbenzene 2) Glass transition temperature (calculated value) of the entire monomer composition Application example 1 Above A-1 and Resin emulsion of A-5, B-1 and B-6, 716.1 parts, acrylic-styrene copolymer resin emulsion (manufactured by Dainippon Ink and Chemicals Co., Ltd., VONCOAT EC-88) as a film-forming resin emulsion
0) 60.1 parts of titanium dioxide/l/ti/I/fi A 71% aqueous dispersion of titanium dioxide was blended as shown in Table 2, and the mixture was added with 1.4 parts of tributyl phosphate, 16.5 parts of water, and Add 0.18 parts of hydroxyethyl cellulose to
In addition, the mixture was stirred until the viscosity became constant.

The resulting paints were coated side by side on morsst masking charts to form a film of the same thickness and air-dried for 3 days. Table 2 shows the physical test conditions for these coatings. 1) Particle size: Measured from a transmission electron micrograph of the emulsion. 2) Mechanical stability: Emulsion, 7509, was measured using a Marlon tester at a load of 10 at 9 x 3,00 rpm. The amount of aggregate produced after 10 minutes of treatment was measured and calculated using the following formula.

(Evaluation) O...(4) is less than 0.1 Δ...(4)
is 0.5- or more 3)/Remer solubility: Add the resin arm after evaporation of water from the emulsion to each solvent and observe (concentration 5%).

(Evaluation) O...does not dissolve ×...dissolves 4) Light transmittance of paint film 2 After leaving the prepared paint for one day, it was applied to a glass plate with a 3 mil applicator, and 23'C, 65 After drying in RH for 1 day, it was measured at 90'/O' using a Murakami gloss meter.

5) Gloss (Glass plate) 2 After the prepared paint was left for one day, it was applied to a glass plate using a 3 mil aggregator, dried for one day at 23°C and 65% RH, and then measured using a Murakami gloss meter.

6) Gloss 2 After leaving the created paint for a day, hide it (
1 "Ratio test m') - Apply to a test paper using an applicator and measure with a Murakami gloss meter after drying for 5 days at 23° C. and 65% RH.

7) Measure the 45'100 gloss of the coating film with opacity 2 and 6) on the black and white areas of opacity test paper (Nippon Test, manufactured by Otonel Kogyo Co., Ltd.), and calculate the ratio by using the formula below. (JIS K-5400).

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 judged visually.

(Review 1iffi) O...No swelling, Pristaritz 1
Partial Δ... Swelling cloth, 〃 X91. Large swelling and blistering 9) After water resistance test = After the test in 8), the gloss of the coating film was measured using a Murakami gloss retention type gloss meter, and is expressed as a percentage of the gloss in 5).

10) Alkali resistance: After drying the glass plate coating film prepared in 5) for one day, it was immersed in a 2% NaOH, saturated Cm(OH)2 aqueous solution for 14 days, and the condition of the coating film was visually judged.

(Evaluation) O...Swelling cloth, no blistering X...
・l 1 Blistering 11) Alkali resistance test: tD gloss retention after coating after the alkali resistance test in 10) Dry at room temperature for 2 days to achieve gloss (60o/60Q)
All measurements were taken and expressed as a percentage of 5) gloss.

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

(Evaluation → ○...No peeling of paint film after 2000 timesΔ...
Peel off the coating after 1000 to 2000 times...100
13) Weather resistance: The prepared paint was applied to a slate board twice with a brush and dried for 7 days before being tested.

Visually judge the condition after 6 months of exposure.

(Evaluation) After drying the slate board coating film created with (FF (i [[l) O...Good Δ... Average X... Poor 14) Accelerated weather resistance: 13] for 7 days, (Evaluation) ...Good Δ... Fair A water-based paint composition was obtained in the same manner as the paint &Q of Application Example 1. Its physical properties are shown in Table 3. Similarly, each coating composition has a solid content concentration of 46
．． 1%, PVC 27.3%, and PWC 39.4%.

, /' 1/ Table 3 Application example 2 A-1 and the commercially available resin emulsion, namely Rho
plex-OP-42 (acrylic-styrene copolymer resin emulsion, solid content 40.8%, Rohm & Ha
As company! 8ri, 5plndrl? t (Polyester resin emulsion, solid content 29.6%, Encaps
(manufactured by Ulalr Inc.), Lytoron2202
(Styrenic resin emulsion, solid content 47.1%, m
+) Hant (manufactured by one company), Plastic Pigm@
nt 722 (styrenic resin emulsion, solid content 4
40% each (manufactured by Dow Chemica 1)
(solid content) of aqueous acrylic-styrene emulsion (
Dainippon Ink and Chemicals Co., Ltd. IJ VONCOAT
5460) 60 parts, tributyl phosphate 1.4 parts,
16.5 parts of water and 0.1 parts of hydroxyethyl heptalulose
8 parts were added slowly and the mixture was stirred until its viscosity was constant.

The above-mentioned various paints were applied onto a mors@st masking chart and a glass plate, and air-dried for 3 days to form a coating film of the same thickness. Table 4 shows the properties of these emulsions and the physical properties of the coating films.

In addition, the solid content of each paint arjL43. o%, PVC40,
0.

FWC39.0%.

Application Example 3 The emulsion aqueous solutions of fcA-IPA-5F obtained in Examples 6 to 10 and B-1, B-2, and B-3 obtained in the comparative example were powdered to produce B-IP and B-3, respectively. 2
7.7 parts each of P and B-3P, as a film-forming resin emulsion, acrylic-styrene copolymer resin emulsion)-J
No (Inu Nippon Ink Chemical Industry Co., Ltd.), VONCOAT
EC-880) 60.1 parts and 16.6 parts of a 71% aqueous dispersion of rutile titanium dioxide were blended, and the mixture was mixed with 1.4 parts of tributyl phosphate, 24.9 parts of water, and 0.18 parts of hydroxyethyl cellulose. The mixture was added slowly and stirred until the viscosity became constant.

The obtained paints were applied side by side in a hiding power chart to form a coating film of the same thickness 3
Air-dried for days. Table 6 shows the physical chemistry of these coatings a″JJ
Characterized.

Application example 1 paint store] and paint A3, 4, application Fig.
Each of the paints in Example 3 (1) was applied to a glass plate, kept at room temperature for - weeks, and then dried at 50°C for 24 hours.
iv immersed in liquid nitrogen to freeze and then rupture
The T-plane was observed with a scanning electron microscope, and each #
Photographs with T side as figures 1 to 4 (magnification: X5000X2
/'3). The hollow-looking particles in Figures 1 and 4 are non-film-forming vinyl resin particles.

[Brief explanation of the drawing]

Figures 1 to 4 are Example 1, Comparative Example 1, and Kasumi, respectively.
2, 6, and 6 are electron micrographs showing the cross-sectional state of the coating films obtained by immersing them in liquid nitrogen and observing the cross-sections after freezing with a scanning electron microscope. . Figure-1: Paint join // 2: N 43 //3: //A4 //4: #A■

Claims (2)

[Claims] (1) A water/oil/water (W/O/W) type composite emulsion is obtained from a polymerizable vinyl monomer, a lipophilic emulsifier, a hydrophilic emulsifier, and water, and then the polymerizable vinyl monomer is polymerized. A method for producing a non-film-forming vinyl resin emulsion having small pores inside. (2) Obtain a water/oil/water (W/O/W) type composite emulsion consisting of a polymerizable vinyl monomer, a lipophilic emulsifier, a hydrophilic emulsifier, and water, and then add the polymerizable vinyl monomer. A method for powdering a non-film-forming vinyl resin emulsion having small pores inside, which comprises polymerizing and then powdering.