JPS6279202A - Production of non-film-forming resin emulsion and method for pulverizing same - Google Patents

Abstract

PURPOSE:To obtain an emulsion having excellent masking property and giving a coating film having excellent gloss, water-resistance, alkali-resistance, etc., when added to a paint, etc., by adding a specific radically polymerizable monomer to an emulsion of an emulsion-polymerized polymer and carrying out the emulsion-polymerization of the monomer. CONSTITUTION:An emulsion of an emulsion-polymerized polymer is added with one or more kinds of radically polymerizable monomers capable of forming a polymer having a contact angle with water of larger than that of the polymer of the above emulsion (preferably having a contact angle of 30-90 deg. with water) by 1-110 deg., preferably by 5-90 deg. and the monomer is subjected to emulsion polymerization to obtain a non-film-forming resin emulsion having small hole in the emulsion particle. The polymer for forming the emulsion of an emulsion- polymerized polymer is a polymer containing a vinyl monomer having hydrophilic group, (1-4C) alkyl (meth)acrylate or polyfunctional crosslinkable monomer, and the monomer to be added to the emulsion is preferably an olefin, monoene, diene or polyfunctional crosslinkable monomer having relatively high hydrophobic property. The emulsion can be easily pulverized e.g. by drying.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a non-film-forming resin emulsion having small pores inside that is useful for various coating agents such as paints, paper, textiles, and leather, and various additives. 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 materials are described in Australian Patent No. M455277. That is, an aqueous pigment dispersion is suspended by 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, and then A water-soluble polymer such as a non-film-forming resin emulsion with small pores stabilized by adding partially hydrolyzed I or vinyl acetate, or an unsaturated polyester resin having a polyethylene oxide chain is used, and water-bathable polymers are used. An improved version of the above emulsions without the addition of coagulants (% 1977-12948)
No. 5 Specification Reference 9) has been proposed. However, although coating compositions using these non-film-forming resin coatings have excellent hiding properties, they have the drawback of producing coatings with no discernible gloss.

Also, the one made of vinyl resin is US Patent No. 315228.
This is proposed in the specification of No. 0. That is, when producing a non-mobile vinyl resin emulsion having small pores, α, β-ethylenically unsaturated carboxylic acid or salts thereof are used as a core particle as a monomer, and at least 5 or more polymers are used. Using the polymerized product, at least one monoethylenically unsaturated monomer is added to form a sheath polymer on the core granules, and after polymerization, the core polymer is neutralized and swollen with an aqueous volatile base. This is a method for producing a non-film-forming emulsion with small pores. A coating composition using such a non-film-forming resin emulsion of an aqueous volatile base-neutralized swelling base has hiding properties, but has poor gloss and is particularly weather resistant.

Difficulties are recognized in durability such as alkali resistance.

There is also a method for producing a non-film-forming resin emulsion having small pores without using a carbonic acid monomer as described above (
J,Polym,Sci,,Polym,Latt,
Edn,.

19.143 (1981)) has also been proposed. That is, styrene is emulsion polymerized on core particles of an emulsion of polymethyl methacrylate to form a styrene polymer. In this case, the non-volatile content is 15 with a core-sheath ratio of l:2.
% non-film-forming resin emulsion 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, and is therefore impractical in terms of miscibility and mechanical stability when blending one component.

[Problem that the invention seeks to solve]

The present invention provides (1) a non-film-forming resin emulsion or its powder 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. 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 diligently studied 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, resulting in the invention. .

That is, the present invention involves adding to an emulsion polymer emulsion at least one radically polymerizable monomer capable of forming a polymer having a water contact angle 1 to 110 degrees higher than that of the polymer in the emulsion, and carrying out emulsion polymerization. A method for producing a non-film-forming resin emulsion having small pores inside, and the non-film-forming resin emulsion.

The present invention provides a powdering method for powder.

The emulsion polymer emulsion used in the present invention is usually obtained by emulsion polymerization of radically polymerizable monomers, and when the polymer does not contain additives such as emulsifiers, the contact angle of water is 25. ~110°.

More selectively, it is preferably 30 to 90'.

As the radically polymerizable monomer constituting the emulsion polymer emulsion, the following monomers may be used alone or in any mixture.

(1) Carxyl group-containing monovinyl monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include maleic acid, fumaric acid, etc., but it is recommended to use 5% by weight or less, preferably 4.5% by weight or less, more preferably 3.5% by weight or less, based on the total monomers, for better water resistance and alkali resistance. This is preferable because it can provide a non-film-forming resin with improved film resistance.

(2) Hydroxyl group-containing monovinyl monomers such as 2-hydroxyethyl acrylate, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Examples include ε-droxyglovir methacrylate, hydroxybutyl acrylate, allyl alcohol, methalyl alcohol, and the like.

(3) Monovinyl monomers containing an amide group, an N-methylol group thereof, or an alkoxy group thereof, such as (meth)acrylamide, N-methylolated (meth)acrylamide, and the like.

(4) Nitrile group-containing monovinyl monomers such as acrylonitrile and methacrylate trile.

(5) Nitrogen-containing alkyl group-containing monovinyl monomers, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like.

(6) Monovinyl monomers containing sulfonic acid groups or bases thereof, such as peel sulfonic acid, styrene sulfonic acid, and salts thereof.

(7) (Meth)acrylic acid alkyl esters such as methyl-, ethyl-, glopyru-, n-butyl-1t-butyl-1n-amyl-11-amyl-, hexyl-, octyl-, nonyl-, decyl-, dodecyl- , octadecyl-, cyclohexyl-, phenyl-1pe/zyl (meth)acrylate, and the like.

(8) Monovinyl ester side-lights include vinyl acetate, vinyl propionate, vinyl butyrad, persati, vinyl phosphate, and the like.

(9) Monovinyl ether examples, t hamethyl-, ethyl-, glopyru-, butyl-
, amyl, hexyl vinyl ether and the like.

Other monovinyl monomers such as vinyl halides such as vinyl chloride or vinylidene chloride; or unsaturated dibasic acid sialkyl esters such as sialkyl esters of maleic, fumaric or itaconic acids, styrene or Kistyrenes such as vinyltoluene; monoenes and dienes such as ethylene and butadiene; monovinyl monomers containing silane groups such as vinyltrichlorosilane/vinyltriethoxysilane; glycityl group-containing such as (methyl)glycidyl (meth)acrylate Examples include monovinyl monomers.

α or polyfunctional crosslinkable monomer having two or more polymerizable unsaturated bonds in the molecule, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate , propylene glycol no methacrylate, cyhinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol zoacrylate), 1,3-butylene glycol no acrylate, and the like. The amount of the polyfunctional crosslinkable monomer to be used is preferably less than 50% by weight, preferably 0.1 to 30% by weight based on the total monomers, considering the solvent resistance of the final resin.

The above-mentioned emulsion polymer emulsion serves as seed particles when producing a non-film-forming resin emulsion, and the radically polymerizable monomer added to the emulsion polymer emulsion is produced thereby. The contact angle of water of the polymer is 1 to 110° compared to that of the polymer of the emulsion polymer emulsion.
, preferably 5 to 90 degrees higher. Such a radically polymerizable monomer can be appropriately selected from the radically polymerizable monomers constituting the emulsified polymer emulsion (W) used as the seed particles.

In the present invention, the radically polymerizable monomer constituting the emulsion polymer emulsion and the radically polymerizable monomer to be added later can be arbitrarily selected as long as they satisfy the above conditions. The Lanocal polymer constituting W-N is a hydrophilic group-containing vinyl monomer, C1 of (meth)acrylic acid,
It is preferable to include a C4 alkyl ester and a polyfunctional crosslinkable monomer, and the post-added polymerizable monomer (monomer forming the second stage) is a relatively hydrophobic olefin such as styrene or vinyltoluene. etc.: It is preferable to include monoenes and dienes such as ethylene and butadiene, and polyfunctional crosslinkable monomers.

The polymer produced by the post-added radically polymerizable monomer has lower hydrophilicity than the polymer of the emulsion of the seed particle, and its contact angle with water usually does not exceed 1200.

In the present invention, the contact angle of water on a polymer is defined as the contact angle between water droplets and the film or sheet when a drop of water is dropped on the film or sheet of the polymer in a state where the polymer does not substantially contain additives such as emulsifiers. It is shown in terms of the contact angle. The contact angle is described, for example, in "Medical Materials and Living Organisms" edited by Manabu Seno, Yukio Imanishi, Yoshi Takemoto, and Hisashi Sakurai, published by Kodansha Publishing.

In the production method of the present invention, the amount of emulsion polymer emulsion used is determined by its solid content/later added lanocal polymerizable monomer(s).
rLii ratio 0.1/99.9 to 90/10. Preferably, 0.5/99.5 to 20/80 is appropriate.

When producing a non-film-forming vinyl resin emulsion,
Emulsifiers and catalysts are usually used. Examples of the emulsifiers used include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances with surfactant ability such as acrylic oligomers, and these can be used alone or in combination of 2s or more. Of these,
Nonionic and anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. As the nonionic emulsifier, any commercially available nonionic emulsifier such as polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, etc. can be used. Further, as the anionic emulsifier, any of commercially available anionic emulsifiers such as alkylbenzene sulfonic acid alkali salts, alkyl sulfate alkali salts, and I-lyoxyethylene 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, and in particular, polycarzonic acid or sulfo/acid salts are commercially available, so they can easily be used. 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 resulting emulsion becomes larger and the hiding properties become better. If so, the amount should be 5 parts by weight or less, preferably 2 parts by weight or less, per 100 parts of total leather mass.

Note that emulsifiers are always used during the production of emulsion polymer emulsions that serve as seed particles, but they may or may not be added during subsequent polymerization, and it is usually preferable not to add them. is preferred. The amount of emulsifier used is not particularly limited, but is usually 0.00 parts per 100 parts by weight of the total emulsifier.
It is about 1 to 10 parts by weight.

In addition, as a catalyst, any catalyst commonly used in emulsion polymerization may be used; typical examples include hydrogen peroxide, water-soluble inorganic peroxides such as ammonium persulfate, or persulfate; Organic peroxides such as hydro-A-oxide and benzoyl gloss oxide; azo compounds such as azobisisobutyronitrile; these may be used alone or as a mixture of two or more. The amount used is 0.1 based on the total weight of monomers.
It is about 2 inches.

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.

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

The emulsion polymer emulsion used in the present invention is usually synthesized using the above-mentioned monomer, an emulsifier, a catalyst, etc., and has no internal pores and has a particle size of about 0.01 to 1.0 microns. It is preferable that the solid content of resin particles is 5 to 65'M.

In the present invention, when a radically polymerizable monomer is added to the emulsion polymer emulsion and polymerized, the polymer particles in the emulsion polymer emulsion are swollen with the monomer, and then the emulsion polymerization is carried out. Differences in the hydrophilicity of the polymers result in the formation of an emulsion of non-film-forming resin particles with small pores inside. It is inferred.

The obtained non-film-forming resin emulsion contains core-shaped vinyl resin particles having small pores (microids) inside, and the small pores of the particles are hollow. Also, water may be present.

If water is present within such pores, such water will volatilize during drying. In addition, non-film-forming vinyl resin particles usually have a particle size of 0.1
It has a particle size of ~5.0 microns, preferably 0.2-1.0 microns, and the small pores (microids) inside thereof are usually 0.01-1.0 microns, preferably 0.2 microns. It has a diameter of ~0.5 micron.

The solid content concentration of the non-film-forming resin emulsion of the present invention is not particularly limited, but is generally 5 to 70% by weight, preferably 2% by weight.
0 to 60% by weight is suitable. If the amount is less than 5% by weight, the hiding property is insufficient, and if it exceeds 70% by weight, manufacturing becomes difficult.

Note that it can be easily confirmed whether the core-shaped resin particles of the non-film-forming 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.

In the present invention, the non-film-forming resin emulsion described above can be powdered by drying.

Powdering can be carried out by any commonly used emulsion powdering 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 moving bed drying. It can be done with The solid content concentration of the emulsion before drying is preferably about 20 to 60% by weight.

The particle size of the obtained non-film-forming resin powder is almost the same as that 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.

[Action/Effect]

The non-film-forming resin emulsion and its powder obtained in the present invention have excellent hiding properties, and when added to paints, for example, they produce coatings with excellent physical properties such as gloss, water resistance, alkali resistance, and weather resistance. be able to. In particular, addition of titanium oxide in an amount smaller than that generally added to paints further increases the hiding power and produces a coating film with high gloss retention.

In addition to paints, such emulsions and powders can also be used as paper coatings,
The powder can be added to various things such as inks, adhesives, pressure-sensitive adhesives, leather sealants, primers, and abrasion resistance improvers for textiles. It is mixed with molding resin such as polypropylene and molded into miscellaneous goods, toys, industrial parts, electrical parts, etc. Furthermore, when applied to paper or cloth,
It can produce artificial leather, rugs, clothing, waterproof sheets, etc., and when applied to metal plates, it can produce corrosion-resistant metal plates (f-record metal).

〔Example〕

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

Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of water and 2 parts of emulsifier (1.0 part of Emuldan 120 and 1.0 part of Emal 20A manufactured by Kao Sekiken Co., Ltd.) were added. part) and stirred well. Next, the reaction vessel was kept at an internal temperature of 80°C, and a mixture of 12 parts of styrene, 7 parts of methyl methacrylate, 6 parts of acrylonitrile, and 0.4 parts of ethylene glycol dimethacrylate, 0.05 parts of ammonium persulfate, and 4 parts of water The mixture was injected for about 1 hour to react, and was further aged for 1 hour.

Thereafter, while maintaining the internal temperature at 80°C, a mixture of 50 parts of styrene, 28.5 parts of p-methylstyrene, and 1.5 parts of divinylbenzene, and a mixture of 25 parts of ammonium persulfate and 5 parts of water were injected over about 1 hour. React and further mature for 45 minutes
I went for a minute. Then cool.

Add 1.0 part of 25 thiammonia aqueous solution to 8.8
The obtained emulsion had a solid content concentration of 48.6%, a viscosity of 13 ape (values measured using a BM-type rotary viscometer, rotor boiling 1, rotation speed 60 rpm, temperature 25°C), pH 8.8,
Submicron particle analyzer (Coult@r@N-
4) and an average particle diameter of 0.5μ measured using an electron microscope.
m, micro in particles? The diameter of the id was 0.2 μm.

This emulsion is designated as A-1.

Example 2 In a reaction vessel similar to A-1 above, 100 parts of water and 2 parts of emulsifier (0.5 part of Emuldan 920, Hytenol N-
Add 1.5 parts of Styrene 08) and keep the internal temperature at 70℃.
0 parts of methyl methacrylate, 4.5 parts of glycitul methacrylate, 0.25 parts of acrylic acid, a mixture of 0.1 parts of ammonium persulfate and 3 parts of water, 0.1 parts of sodium pyrosulfite and 3 parts of water. Each portion of the mixture was injected for about 1 hour to react, and was further aged for 1 hour. Thereafter, the internal temperature was maintained at 80°C, and a mixture of 55 parts of styrene, 25 parts of p-methylstyrene, and 5 parts of divinylbenzene,
A mixture of 2 parts of ammonium sulfate and 5 parts of water and a mixture of 0.2 parts of sodium pyrosulfite and 5M of water were each injected over a period of 2 hours, reacted at 70°C, and further aged for 45 minutes. After that, cool the 25 thiammonia aqueous solution 2.
I added the part and adjusted the voice to 8.3.

The obtained emulsion had a solid content concentration of 46.6%, a viscosity of 16 cps, a pH of 8.5, and an average particle size of 0.4 as measured using a submicron particle analyzer and an electron microscope. The sail diameter was 15 μm. Let this emulsion be Person-2.

Example 3 100 g of water (! and 2 parts of emulsifier (5 parts of Emuldan 120 and 1.5 parts of Hytenol N-08) were placed in a reaction vessel similar to A-2 above, and the internal temperature was raised to 70°C. A mixture of 0.1 part of ammonium persulfate and 5 parts of water, a mixture of 0.1 part of sodium pyrosulfite and 5 parts of water, 10 parts of styrene, 4.5 parts of ethyl methacrylate, 0 parts of acrylic acid
．． A mixture of 25 parts of N-methylolacrylamide and 0.25 parts of N-methylolacrylamide was injected over about 1 hour to react, and the mixture was further aged for 1 hour. The product was then added to 75 parts of styrene, 9 parts of methyl methacrylate, 0.5 part of acrylic acid, and glycidyl°.
A mixture of 0.5 parts of methacrylate, a mixture of 0.2 parts of ammonium persulfate and 5 parts of water, and a mixture of 0.2 parts of sodium monosulfite and 5 parts of water were each injected over 2 hours and allowed to react at 70°C. , aged for 1 hour.

Then, the mixture was cooled and 25% of ammonia water was added to adjust the pH, thereby obtaining a resin emulsion. The obtained emulsion is A
-3, and its properties are shown in Table 1.

Example 4 In a reaction vessel similar to A-2 above, 100 parts of water and 3 parts of emulsifier (1.5 parts of Emul p/120 and Hytenol N-
A mixture of 2 parts of potassium persulfate and 5 parts of water and 25 parts of styrene were added, keeping the internal temperature at 80°C.
15 parts of methyl methacrylate, 1.5 parts of acrylic acid, N
A mixture of 1.5 parts of methylol acrylamide was injected and reacted for about 2 hours each, and was aged for an additional hour.

Next, in the resulting emulsion, 40 parts of styrene, 15 parts of α-methylstyrene, 1 part of novinylbenzene, and 1 part of acrylic acid were added.
and a mixture of 0.2 parts of potassium persulfate and 5 parts of water were each injected over 2 hours to react at 80°C.
After aging for a period of time, the mixture was cooled and adjusted to obtain a resin emulsion. The obtained emulsion was designated as A-4, and its properties are shown in Table 1.

Example 5 100 parts of water and 2 parts of emulsifier were added to the reaction vessel as in A-2 above.
part (1.0 part of Emaldan 120 and Hitenol N-0
8), and kept the internal temperature at 50°C, and added a mixture of 0.2 parts of ammonium persulfate and 5 parts of water, a mixture of 0.2 parts of sodium sulfite and 5 parts of water, and t- 10 parts of butyl acrylate, 5 parts of methyl methacrylate, r-
A mixture of 0.5 part of methacryloxypropyltrimethoxysilane was injected over 1 hour to react, and the mixture was further aged for 1 hour.

The resulting emulsion was then mixed with a mixture of 80 parts of styrene, 4 parts of n-butyl acrylate, 0.5 parts of ethylene glycol dimethacrylate, a mixture of 70.2 parts of ammonium persulfate, 5 parts of water, and 0.2 parts of pyrosulfite.
A mixture of 5 parts and 5 parts of water was injected over a period of 2 hours, reacted at 50°C, aged for 1 hour, cooled and pH adjusted to obtain a resin emulsion. This emulsion was designated as A-5, and its properties are shown in Table 1.

Examples 6 to 10 Production example A except that 0.2 parts of an emulsifier (Levenol Wz manufactured by Kao Soap Co., Ltd.) was added to the aqueous phase during the post-polymerization in A-1 to A-5 above. Resin emulsions were obtained in exactly the same manner as in -1 to A-5.

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-
It is 10. The properties of each emulsion are shown in Table 1.

Comparative Example 1 100 parts of water and 2 parts of emulsifier (A
-1) and stir well, add a mixture of 7 parts of tyl methacrylate, 0.6 parts of acrylonitrile, 0.4 parts of ethylene glycol dimethacrylate, 1.5 parts of divinylbenzene, 0.5 parts of ammonium persulfate and 5 parts of water. The mixture was injected in about 2 hours and aged for an additional hour. After that, the resin emulsion (A'-1) was cooled and adjusted.
) was obtained.

Table 1 shows the properties of this emulsion.

Comparative Examples 2 to 5 The emulsifiers and monomers used in A-2, 3, 4, and 5 above were charged in batches and polymerized for about 4 hours by homogeneous copolymerization, and then cooled to form each resin emulzon (A-2). '
-2 to 5) were obtained. The respective correspondences are A'-2 and A
-2, A'-3 and A-3, A'-4 and A-4 and A'
-5 and A-5.

Comparative Example 6 Obtained by the first half method of A-1, that is, 12 parts of styrene, 7 parts of methyl methacrylate as monomers,
Co-x combination emulsion using 16 parts of acrylonitrile and 0.4 parts of ethylene glycol dimethacrylate (
1) Using the same emulsifier as used in (1), 50 parts of styrene, 28.5 parts of p-methylstyrene,
A resin emulsion A'-6 was obtained by blending the copolymer emulsion (II) obtained by polymerizing 1.5 parts of divinylbenzene at a solid content weight ratio of 20:80.

Comparative Example 7 100 parts of water and emulsifier 2B were placed in the same reaction vessel as A-1 above.
(S (1 part of Emaldan 120 and 1 part of Emal 20A) was added and stirred well. Next, the reaction vessel was kept at 80°C and 50 parts of styrene, 28.5 parts of p-methylstyrene, and 1.5 parts of divinylbenzene were added. A mixture of 0.25 parts of ammonium persulfate and 5 parts of water was injected over about 1 hour to react, and the mixture was further aged for 1 hour.Then, the internal temperature was kept at 80°C and 12 parts of styrene and 7 parts of methyl methacrylate were added.
A mixture of 0.6 parts of acrylonitrile and 0.4 parts of ethylene glycol dimethacrylate, and a mixture of 4 parts of ammonium persulfate O,OS and 4 parts of water were injected over about 1 hour to react, and further aged for 45 minutes. Ta.

Thereafter, it was cooled, and 1.0 part of a 25% ammonia aqueous solution was added to adjust the voice to 8.7.

1) Mo/? Composition: AN...acrylonitrile, n-B
A...-butyl acrylate), St... styrene, MIVtA... methacrylic acid, t-BMA.
...t-butyl methacrylate, GMA...glycidyl methacrylate, EGDM...ethylene glycol diacrylate, p-MS t...p-methylstyrene, 5-butyl methacrylate, α-Mst
...α-methylstyrene, KBM-503...γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.'), DVB...sopinylbenzene 2)
'EC antenna angle,: Contact angle between the first stage copolymer polymer and water droplet D2: Contact angle between the second stage copolymer polymer and water droplet 3) D2-D,: Contact angle between the second stage copolymer polymer and water droplet Difference in contact angle between the copolymer polymer and the first stage copolymer polymer Contact angle of water droplet: Measure the contact angle of a water droplet on the Brimer solid surface using an ermagoniometer type contact angle measuring device rw: Surface tension of water dynI Tan-1r8: Solid surface free energy erg tMI4), glass transition temperature (calculated value) of the entire gel J mer composition Comparative Example 8 (1st stage reaction) In a reaction vessel similar to Example 1, 2900 parts of water and dodecyl sulfonate were added. 2.0 parts of sodium benzene was added and stirred thoroughly. Next, the reaction vessel was heated and the internal temperature was maintained at 80°C. Fifty parts of a monomer emulsion prepared from 266 parts of water, 40 parts of sodium dorsylbenzene sulfonate, 416 parts of butyl methacrylate, 374 parts of methyl methacrylate, and 10.4 parts of methacrylic acid was added to the reaction vessel and then 3 parts ammonium persulfate dissolved in 101717 water was added. After 15 minutes, dropwise addition of the remaining monomer emulsion at 16 parts/min was started. Reaction temperature to 8
The reaction mixture was raised to 5° C. to react, and 15 minutes after completion of the dropwise addition, the reaction mixture was cooled. Thereafter, 25% ammonia aqueous solution was added to adjust - to 9.4.

The resulting emulsion had a solid content concentration of 19.5 μm and an average particle size of 0.095 μm.

(Second stage reaction) In a reaction vessel similar to the first stage reaction, 2115 parts of water and 2 parts of water were added.
4.2 parts of ammonium per(iii!) acid dissolved in
2 parts were added. 235 parts of water, 0.8 parts of sodium dodecylbenzene sulfonate, 490 parts of methyl methacrylate,
A monomer emulsion consisting of 210 parts of methacrylic acid and 3.5 parts of ethylene glycol diacrylate was poured into a reaction vessel at 985°C for 3 hours to react, and was further aged for 30 minutes. The emulsion that was then cooled had a pH of 2.3, a solids concentration of 22.4%, and an average particle size of 0.35 microns. The diluted sample of the dispersion was neutralized to pH 10 with 25% thiammonia.

As a result of an electron microscope test, the average particle diameter was 0.8 microns, which corresponded to swelling of about 12 times the volume.

(Third stage reaction) 0.07 parts of ammonium persulfate was added to 80 parts of water heated to 85°C in the same reaction vessel as in the first stage reaction, and then 4.5 parts of the polymer dispersion for the second stage reaction. (1 part solid polymer) was added. A mixture of 12 parts of methyl methacrylate, 6 parts of inbutyl methacrylate and 2 parts of methacrylic acid was added over a period of 1 hour while maintaining the temperature at 85°C. The temperature is 85℃ until 98 or more of the monomers have reacted.
was held at After cooling, it was neutralized with an aqueous solution of 25 thiammonia, and the neutralized dispersion was heated to 95° C. for 1 hour and cooled to room temperature. As a result of an electron microscope test, the average particle diameter was swelled to 1.1 s microns. The average pore diameter was 0.8 microns.

Note that the obtained emulsion is designated as A'-8.

Application example 1 A-1 of Example 1, A-6 of Example 6, A' of Comparative example 1
-1, A'-2 of Comparative Example 2, A/-7 of Comparative Example 7, and A'-8 of Comparative Example 8, 716.1 parts of each emulzo resin,
As a film-forming resin emulsion, acrylic-styrene copolymer resin emulsion (V manufactured by Inu Nippon Ink Chemical Industry Co., Ltd.)
60.1 parts of ONCOAT EC-880) and a 71% aqueous dispersion of rutile titanium dioxide were blended as shown in Table 2, and 1.4 parts of tributyl phosphate and 16 parts of water were added to the mixture.
．． 5 parts of hydroxyethyl cellulose and 0.18 parts of hydroxyethyl cellulose were added thereto and stirred until the viscosity became constant.

Each of the obtained paints was applied side by side on a Mor@mt hiding power chart to form an a film of the same thickness and air-dried for 3 days. Table 2 shows the physicochemical properties of these coatings.

7-' Test conditions 1) Particle size: ■ Measured from a scanning electron micrograph of the emulsion ■ Measured by submicron particle analyzer (Coulter mode I N-4) 2) Mechanical stability: Emulsion 1-50I was measured using Marlon The amount of aggregate produced was measured using a testing machine under a load of 10 kg and 3,000 rpm for 10 minutes, and calculated using the following formula.

(If value) O...The concentration is less than 0.1 Δ...(The sword is 0.5% or more 3) Polymer solubility: Add the resin powder after water evaporation of the emulsion to each solvent and observe (concentration 5chi).

(Evaluation) ○...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, After drying in RH for one day, it was measured with a Murakami gloss meter at 90° and 10°.

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

Apply at 23℃, 65℃ Murakami style after drying in Chi RH for 5 days Measured with a gloss meter.

7) The gloss at 45° 10' of the coating film with opacity ratio 2 6) was measured on the black and white areas of opacity test paper (manufactured by Nippon Test Panel Kogyo ■), and the ratio was calculated using the formula below (JIS K -5400).

8) Water resistance: After drying the glass plate coating film prepared in 4) for one day, it was immersed in water at room temperature for 14 days and visually determined.

(Evaluation) ○...We@None, Blistering Part 1 II
FΔ...Swelling @ present, ×...High swelling, expressed as a percentage of pristalling.

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

(Evaluation) O...Swelling, no pristalling X...
- Swelling and pristalling (60°/60°) were measured and expressed as a percentage of the gloss in 5).

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

(Evaluation) O... No peeling of paint film after 2000 times Δ...
The paint film peeled off after 1000 to 2000 times...100
The paint film peeled off after less than 0 times. 13) Weather resistance 2 The prepared paint was applied to a slate board twice with a brush and dried for 7 days before testing.

Visually judge the condition after 6 months of exposure.

(Evaluation) ○... Good Δ... Fair Good Δ... Average ×... Bad Application Example 2 A-2 to 5 and A-7 to 1 obtained in the above Examples and Comparative Examples
16.1 parts of each emulsion of A'-0 and A'-2 to A'-5, 60 parts of an aqueous acrylic-styrene emulsion (manufactured by Dainippon Ink & Chemicals, VONCOAT 5460) and 16.1 parts of an aqueous dispersion of rutile titanium dioxide. 58 parts were added. 1.4 s of tributyl phosphate, 16.5 parts of water and 0.18 parts of hydroxyethyl cellulose were slowly added and the mixture was stirred until its viscosity became constant.

The above-mentioned various paints were applied side by side on a morest masking chart and a glass plate to form a 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 is 27.3 volume and PWCij 39.
It is 4%.

Application Example 3 Example 1 A-1 and a commercially available resin emulsion, namely Ropaque-OP-42 (acrylic-styrene copolymer resin emulsion, solid content 40.8%, Roh
m & Haas), 5pindrift (n
! Reester resin emulsion solid content 29.6%,
Encapsulair Inc.), Lytoron
2202 (Styrenic resin emulsion, solid content 4
7.1 inch, manufactured by monaanto), Plastic
Pigment 722 (styrenic resin emulsion, solid content 49.3%, manufactured by Dow Chemica 1) was added to each 40 s (solid content) of aqueous acrylic-styrene emulsion (VONCOAT manufactured by Dainippon Ink & Chemicals).
5460) 60 parts, Rinshun tributyl 1.4 parts,
16.5 parts of water and 0.1 parts of hydroxyethylcellulose
8 parts were added slowly and the mixture was stirred in a well to keep the viscosity constant.

The above-mentioned various paints were applied on a moreat covert cover 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 coatings, PWC 39.0%.

Examples 11 to 16 A-1, A-2, A-3, A-4 synthesized in the above examples
, A-5, and A-6 at an inlet temperature of 150 ~
200°C and dropping rate 2. A resin powder was obtained in 3 hours under the condition of Ol/hr.

Table 5 shows the characteristics of each resin powder obtained.

Note) The parentheses in polymer solubility indicate the glue fraction (-).

Note 1) Particle size: Measured from a scanning electron micrograph of fine powder 2) Heat content % Temperature: From differential thermal analysis in N2 3) Polymer solubility: Fine powder IIi was measured three times in each solvent 10- Calculate the polymer glue fraction using the following formula from the residual powder weight (, F) after washing (centrifugal 1 hr). Glue fraction (a) = (residual powder type f/
Emul-)W powder) xi 00#x-y=bow-゛Application example 4 7.7 parts of each resin powder obtained in Examples 11 to 16, acrylic-styrene resin Emulsilon (Dainippon Ink & Chemicals)
60.1 parts of VONCOAT EC-880 (manufactured by VONCOAT EC-880) and 1666 parts of a 71% aqueous dispersion of rutile titanium dioxide, and to the mixture were added 4 parts of tributyl phosphate L and 24.1 parts of water.
9 parts of hydroxyethyl cellulose and 0.18 parts of hydroxyethyl cellulose were slowly added and stirred until the viscosity became constant.

The resulting paints were applied side by side on a moreit masking chart to form a film of the same thickness and air-dried for 3 days. Table 6 shows the physical and chemical properties of these coatings.

7.' Paint A (El) of Application Example 1 (using A-1 non-film-forming resin emulsion bottle), Paint A (1+l) (A'-1 using emulsion bottle), and Paint No. fL(V) (
VONCOAT EC-880 (for convenience only) and Application Example 4 (using non-film-forming resin emulsion) were applied to a gold glass plate, kept at room temperature for - weeks, and then After drying at 50℃ for 24 hours, it was immersed in a liquid solution for KM, and then the fractured cross section was examined with a scanning f-type electron microscope. $:X5000).

In addition, Figures 1 and 4 show small pores obtained in the present invention (hollow non-film-forming resin 8' particles are observed due to the non-film-forming resin emulsion having micro dζ-oids), whereas Figure-2 and 3
cannot accept that.

[Brief explanation of drawings]

Figure-t~4tiSotLere2A(II), (t
ill, (V) Oh! This is an electron micrograph A showing the cross-sectional state of the coating film obtained by immersing the coating film in a liquid base material and observing the cross section of the frozen sickle with a scanning bubble electron microscope arm. Figure-1: Blood J Asahi (It) Figure-2: Paint store song) #3:'(V) '4: #(X[[[)

Claims (1)

[Claims] 1. Adding to an emulsion polymer emulsion at least one radically polymerizable monomer capable of forming a polymer having a water contact angle 1 to 110° higher than that of the polymer of the emulsion. 1. A method for producing a non-film-forming resin emulsion having small pores inside, which comprises emulsion polymerization. 2. Add to the emulsion polymer emulsion at least one radically polymerizable monomer capable of forming a polymer with a water contact angle 1 to 110 degrees higher than that of the polymer in the emulsion, and conduct emulsion polymerization to form an internal polymer. 1. A method for powdering a non-film-forming resin emulsion having small pores inside, the method comprising obtaining a non-film-forming resin emulsion having small pores inside, and then powdering this.