JPS6295301A - Production of non-film-forming resin emulsion used in field other than cosmetic and method for pulverizing said emulsion - Google Patents

Abstract

PURPOSE:To obtain an emulsion having the form of core containing small hole in the particle and having excellent physical properties such as weather- resistance, gloss, masking property, heat-aging resistance, etc., and high practicality, by adding a specific radically polymerizable monomer, etc., to an emulsion- polymerized polymer emulsion and carrying out emulsion-polymerization of the mixture. CONSTITUTION:An emulsion-polymerized polymer emulsion which may contain ultraviolet absorber and/or antioxidant is added with (A) one or more radically polymerizable monomers capable of forming a polymer having a contact angle to water of larger than that of the polymer of the above emulsion by 1-110 deg. (the contact angle to water is preferably 30-90 deg. in a state free from additive, e.g. acrylic acid, vinylsulfonic acid, etc.) and (B) an ultraviolet absorber and/or antioxidant. The mixture is subjected to emulsion-polymerization and, if necessary, pulverization. USE:Useful as a treating agent or additive for a material other than cosmetic, e.g. paint, paper, woven fabric, leather, etc.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to ultraviolet absorbent and/or antioxidant-containing anti-oxidant 1 used as a treatment agent or additive for paints other than cosmetics, paper, textiles, leather, etc. This invention relates to a method for producing a synthetic resin emulsion and a method for pulverizing the same.

[Conventional technology and its top points]

In recent years, methods for producing non-film-forming bead-shaped resin particles having small pores have been proposed. For example, Australian Patent No. 455277 for the ester-based product? It is written in books such as iB. 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-degradable resin emulsion with small pores stabilized by adding polyvinyl acetate that has been partially water-decomposed within a day, or an unsaturated polyester cut resin having polyethylene oxide chains, is used. An improved version of the above emulsion without the addition of polymers (%
485) has been proposed. However, although coating compositions using these non-film-forming resin emulsions have excellent hiding properties, they have the drawback of producing coatings with no visible 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-film-forming vinyl resin emulsion having small pores, α,β-ethylenically unsaturated carboxylic acids or salts thereof are copolymerized as a monomer with a weight ratio of at least 5 or more as core particles. Then, at least one monoethylenically unsaturated sheath monomer forming a sheath polymer is added onto the core granules, and after polymerization, small pores are formed by neutralizing and swelling the core polymer with an aqueous volatile base. This is a method for producing a non-film-forming emulsion. A coating composition using such an aqueous volatile base neutralized swelling non-film-forming resin emulsion has hiding properties but has poor gloss and is particularly weather resistant.

Difficulties are recognized in durability such as 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, Sci, r Polym, Lett,
Edn, .

19.143 (1981)) has also been proposed. In other words, styrene is emulsion-polymerized onto core particles of a polymethyl methacrylate emulsion to form a polymer. In this case, the non-volatile content is 15 with a core-sheath weight ratio of 1:2.
% 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 have sufficient reaction, and is therefore impractical from the viewpoints of miscibility and mechanical stability during paint formulation.

Further, conventional non-film-forming resin emulsions have not been particularly improved in weather resistance or heat aging resistance, and there is a demand for ones with even better performance.

[Means for solving the C apex] The present inventors have developed a core-shaped non-film-forming material with small pores inside that has excellent physical properties such as weather resistance, gloss, hiding property, and heat aging resistance, and is highly practical. As a result of intensive research into a method for producing a vinyl resin emulsion and a method for pulverizing the same, the invention was achieved.

That is, the present invention can form a polymer having a water contact angle 1 to 110 degrees higher than that of the polymer of the emulsion, in an emulsion polymer emulsion that may contain an ultraviolet absorber and/or an antioxidant. A method for producing a non-film-forming resin emulsion for use in products other than cosmetics, which is characterized by emulsion polymerization with the addition of at least one radically polymerizable monomer, an ultraviolet absorber, and/or an antioxidant, and a method for powderizing the same. provide.

The emulsion polymer emulsion, which may contain an ultraviolet absorber and/or an antioxidant, used in the present invention is usually obtained by emulsion polymerization of radically polymerizable monomers. The contact angle of water is 25 to 110 without containing additives such as absorbers, antioxidants, and emulsifiers.
As the radically polymerizable monomer constituting the emulsion polymer emulsion, the following monomers may be used alone or in any mixture.

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

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

(3) A monovinyl monomer containing an amide group or its N-methylol group or its alkoxy group, e.g. (meth)
Acrylic acid amide, N-methylolated (meth)acrylic acid amide, etc. are mentioned.

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

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

(6) Side monovinyl monomers containing sulfonic acid groups or bases thereof include vinyl sulfonic acid, styrene sulfonic acid, and salts thereof.

(7) (Meth)acrylic acid alkyl esters such as methyl-, ethyl-, zolopyl-1n-butyl-1t-butyl-1n-amyl-11-amyl-, hexyl-, octyl-, nonyl-, f-yl-, dodecyl- -, octadecyl-, cyclohexyl-, phenyl-, pentyl (meth)acrylate, and the like.

(8) Phosphate group-containing vinyl monomer side light beam β
-Hydroxyethyl (meth)acrylate α and β
- Condensates of hydroxyalkyl esters of ethylenically unsaturated cargonic acid and phosphoric acid or alkyl phosphoric acids.

(9) Examples of monovinyl esters include tH vinyl acetate, vinyl propionate, buurbutyrate, vinyl persate, and the like.

αQ Monovinyl ethers include, for example, methyl, ethyl, propyl, butyl, amyl, hexyl vinyl ether, and the like.

α◇ Other monovinyl monomers, such as vinyl chloride or vinyl monochloride, such as vinyl chloride; or unsaturated dibasic acids, such as dialkyl esters of maleic acid, fumaric acid, or itaconic acid. noalkoxy esters, styrenes such as styrene modi or vinyltoluene; monoenes and dienes such as ethylene and butadiene; silane group-containing monovinyl monomers such as vinyltrichlorosilane and vinyltriethoxysilane; (methyl)glycidyl (meth) ) monovinyl containing a glycidyl group such as acrylate.

(6) Polyfunctional crosslinkable monomer having two or more polymerizable unsaturated bonds in the molecule, such as 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, 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.

In addition, the emulsion polymer emulsion may contain an ultraviolet absorber and/or an antioxidant, and usually when producing the emulsion, the ultraviolet absorber and/or antioxidant is added to the radical polymerized raw material. is contained in the polymer by adding and then polymerizing. The amount of the ultraviolet absorber and/or antioxidant used may be the amount that dissolves the monomer in 100 parts by weight of the radically polymerizable monomer, but generally 0.01 to 50 parts by weight. Preferably, 0.
More preferably 05 to 30 parts by weight.

Examples of the ultraviolet absorbers and antioxidants include salicylic acid esters such as methyl salicylate, phenyl salicylate, cresyl salicylate, and benzyl salicylate;
-Hydroxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, penzophenones such as 2-aminobenzophenone, 2-(2'-hydroxy- 5'-t-butylphenyl) pen I') azole, 2-(2'-hydroxy/-5'-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'- Benzotriazoles such as metquinphenyl)benzotriazole, 2-(2'-hydroxy-3-5'-di-neopentylphenyl)benzotriazole, ethyl 2-cyano-3,3-sophenyl acrylate, 2- Cyano
2-ethylhexyl 3,3-&phenylacrylate, α
-cyano-β-methyl-4-meth=? Substituted acrylonitriles such as methyl cinnamate, 2,2'-thiobis(4-
octerfelt] nickel complex [, (2,2'-thiobis(4-t-octylphenolate))-n-butylamine di,kel complex salt, etc., p-methoxypennolidan dimethyl malonate, resorcinol Monobenzoic acid ester, hexamethylmonoic acid triamine I',
2.5-i Ultraviolet absorber such as zophenyl-p-pentuquinone; 2,6- , ) -t-7' f /+/-4
-Methylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2- α-Methylcyclohexyl-4,6
- dimethylphenol, hindered monophenols such as styrenated phenol, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol), 4,4
’-bis(2,6-/c-t-butylphenol), 4
．． 4'-Butylidenebis(3-methyl-6-t-butylphenol), 3,5-not-butyl-4-hydroxybenzyl ether, 1.1-bis-(4-hydroxyphenyl)cyclohexane, 4.4' - dioxydiphenyl (4,4'-bisphenol), hindered bisphenols such as 4,4'-isopropylidene-bisphenol, 2,2'-thiobis(4-methyl-6-t-
butylphenol), 2,2'-thiobis(6-methylphenol), 4,4'-thiobis(3-methyl-6-
-butylphenol), 4,4'-thiobis(2,6
-No Ii6 low amyl phenol), bis sulfide (3-
Hindered thiobisphenols such as methyl-4-hydroxy-5-t-butylbenzyl), 2,5-di-t-
Hydroquinones such as butylhydroquinone, 2.5-di-t-amylhydroquinone, 1.3.5-trimethyl-2,4,6-)lis(3,5-di-t-butyl-
Hindered polyphenols such as 4-hydroxybenzyl)benzene and 1,1.3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2.6
-di-t-butyl-4-dimethylaminomethylphenol, N-butyl-p-aminephenol, N-lauroyl-p-aminophenol, N-stearoyl-p-7
Aminophenols such as minophenol, other phenols such as gallic 9f-ropyl, phenyl-α-naphthylamine, N,N'-cyβ-naphthyl-p-phenyldiamine, N,N'-diphenyl-p-phenylenediamine , N,N'-diphenylethylenediamine, N,N
'-Diphenyl-1,2-propylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenecyamine, N,N'-no5ee-butyl-p - Aromatic amines such as -phenylenediamine, N-phenypv -N -(p-toluenesulfonyl)-p-phenylenediamine,
6-nitoxy2.2.4-trimethyl-1,2-dihydroquinoline, 21214-t! J methyl-1,2-
Quinolines such as dihydroquinoline polymers, triphenylphosphite, tris(nonylated phenyl)phosphite, tris-(4-hydroxy-2,5-di-t-
phosphites such as (butylphenyl) phosphite, nickel N,N'-tumethyldithiocarbamate, N
, N-nickel dibutyldithiocarbamate, N,N-
Zinc diethyldithiocarbamate, metal salts of dialkyldithiolupamates such as zinc N-phenylnotiolupamate, dilauryl thiopropionate, 2-
Antioxidants such as mercaptobenzimid f7'-/I/, 2-mercaptobenzimidazole zinc salt, 2-mercaptobenzothiazole zinc salt, isopropylxanthodanate, zinc butylxanthodanate, and the like can be mentioned.

Note that UV absorbers and antioxidants other than those mentioned above can also be used.

The 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 contributes to the formation of the resulting polymer. The contact angle of water 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 mentioned above that constitute the emulsion polymer emulsion used as the seed particles.

In the present invention, the radically polymerizable monomer constituting the emulsion polymer emulsion and the radically polymerizable monomer added later can be arbitrarily selected as long as they satisfy the above-mentioned flexibility. As the radical polymer, hydrophilic group-containing vinyl monomer, (meth)acrylic acid C1~
It is preferable to include a C4 alkyl ester and a polyfunctional crosslinking monomer, and the post-added polymerizable monomer (monomer forming the second stage) is a relatively hydrophobic olefin such as styrene or vinyltoluene. Classes: It is preferable to include monoenes such as ethylene and butadiene, tsenes, and polyfunctional crosslinking monomers.

The polymer produced by the post-added radically polymerizable monomer has lower hydrophilicity than the polymer of the emulsion of the seed particles, and the contact angle of water usually does not exceed 120°.

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 a film or sheet of the polymer in a state where the polymer does not substantially contain any additives such as emulsifiers. It is shown in terms of the contact angle. This contact angle is described, for example, in "Medical Materials and Living Organisms" Manabu Seno, Yukio Imanishi, Yoshi Takemoto, Hisashi Sakurai S Collection, Kodansha Publishing.

In the preparation method of the present invention, the amount of emulsion polymer emulsion used is 1/99.9 to 90/10, preferably 0.5 in terms of solid content/weight ratio of post-added radically polymerizable monomer. /
99.5 to 20/80 is suitable.

Further, as the ultraviolet absorber and/or r/'i antioxidant to be added together with the post-added radically polymerizable monomer, the above-mentioned ones may be used, and the amount added is 100% of the post-added radically polymerizable monomer. The amount dissolved in parts by weight may be sufficient, but preferably 0.01 to 50 parts by weight, more preferably 0.5 to 50 parts by weight.
It is 30 parts by weight.

When producing the emulsion polymer emulsion and non-film-forming resin emulsion in the present invention, it is preferable to use an emulsifier, a catalyst, etc.

Emulsifiers used include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and other reactive emulsifiers.
Substances having surface-active properties such as acrylic oligomers can be mentioned, and these can be used alone or in combination of two or more. Among 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, holoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, etc. can be used, and As the anionic emulsifying agent, any of commercially available anionic emulsifiers such as alkylbenzene sulfonic acid alkali salts, alkyl 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, and in particular, those composed of polycaldic acid or sulfonate salts are commercially available and are readily available. With this, it is also possible to obtain a more so-called soap-free emulsion composition. 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 resulting emulsion has a small particle size and good hiding properties, but the presence of these protective colloids reduces the durability and weather resistance of the compounded coating film. Therefore, when used, the amount should be 5 parts by weight or less, preferably 2 parts by weight or less, per 100 parts by weight of one whole leather.

In addition, when the emulsifier is used during the production of the emulsion polymer emulsion that becomes the seed particles, it may or may not be added newly during the subsequent polymerization, and it is usually preferable not to add it newly. .

In addition, the use of emulsifiers 1 is not limited to one temple, but usually Satoshi $
Chill at about 90.1 to 10 parts by weight per 100 parts by weight.

In addition, any catalyst that is commonly used in emulsion polymerization may be used; typical examples include water-soluble inorganic peroxides or persulfate salts such as hydrogen peroxide and ammonium persulfate; Cumene hydroperoxide, benzoyl! -organic peroxides such as -oxide; azo compounds such as azobisisobutyronitrile; these are used as 17ffi or a mixture of two or more thereof. The amount used is about 0.1 to 2% 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.

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 monomers, emulsifiers, catalysts, etc., and has a particle size of 0.01 to 1.0 microns without small pores inside. It is preferable that the resin particles contain 5 to 65% by weight of resin particles in terms of solid content.

In the present invention, when the radically polymerizable monomer pharyngeal absorber and/or antioxidant 2 is added to the emulsion polymer emulsion and polymerized, such monomers are used to form a polymer in the emulsion polymer emulsion. After swelling, the milk is placed on an upper mold table, and due to the difference in hydrophilicity of each polymer, the polymer of the emulsion polymer emulsion and the polymer that will be produced later are reversed, resulting in a non-film-forming product with small pores inside. It is assumed that an emulsion of resin particles is completely formed.

The obtained non-film-forming resin emulsion contains core-shaped vinyl resin particles having small pores (mic a1f=?id) inside, and the small pores of the particles are hollow. However, water may be present.

If water is present within such pores, such water will volatilize before drying. In addition, the non-film-forming resin particles usually have a particle size of 0.1 to 5.0.
It has a particle size of microns, preferably 0.2 to 1.0 microns, and small pores (micro voids) inside it.
is usually 0.01 to 1.0 micron, preferably 0.02
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 to 1 ton, but is generally 5 to 70 weight percent, preferably 20 to 60 weight percent. The amount required is 5
If the weight is less than 1%, the hiding power is insufficient, and if it exceeds 70% by weight, production 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. In addition, 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.

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 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.

The non-film-forming resin emulsion and its powdered product produced in the present invention are used for purposes other than cosmetics. Next, we will discuss the fields in which it is mainly used.

(Coating Composition) In the case of a non-film-forming resin emulsion, it is used in combination with a film-forming aqueous resin. The film-forming water-based resin to be blended can be used as an inder for general water-based paint compositions such as thin, flat, glossy, elastic, and metal, vinyl resin emulsions, vinyl water-soluble A resin aqueous dispersion, etc. are used. Such resins are usually obtained by polymerizing at least one kind of polymerizable vinyl monomer, and include polymerizable vinyl monomers (t-monomers include styrene, methylstyrene,
Aromatic alkenyl compounds such as α-methylstyrene; methyl-, ethyl-, brol-1n-butyl-1i-butyl-1t-butyl-1n-amyl-5i-amyl-,
hexyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl
Or hapendyl (meth) like acrylate (meth)
Acrylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrald or "vinyl satinate"; methyl, ethyl,
Furopyru, butyl, amyl- also refers to vinyl ethers such as hexyl vinyl ether; vinyl cyanides such as acrylonitrile; Unsaturated dihydrochloric acid dialkyl esters such as dialkyl esters of itaconic acid; α, β
-Ethylenically unsaturated Cal? (meth)acrylamide or its N-methylolated product or its salts; Alkoxylated products; vinyltrichlorosilane and Schiff are silane group-containing α,β-ethylenically unsaturated monomers such as vinyltriethoxysilane; Saturated monomers: ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol diacrylate, 1. Examples include 3-butylene glycol diacrylate, which can be used alone or in combination with
It is also possible to use more than one species in combination.

To produce a vinyl resin emulsion among such film-forming aqueous resins, the above monomers are added dropwise or continuously, either all at once or in portions, usually in the presence of an emulsifier and a catalyst.
This is carried out by polymerization at a temperature of -100°C, preferably 30-90°C. The emulsifier and catalyst used in this case may be those used in the production of a non-film-forming resin emulsion. In addition, the production of the vinyl water-soluble resin involves mixing the hydrophilic monomer of the polymerizable vinyl monomers and other monomers in a water-soluble organic solvent such as methanol or ethanol.
This is carried out by polymerization at 0 to 150°C. Furthermore,
The aqueous vinyl resin dispersion is produced by polymerizing the water-soluble resin using a reduced amount of hydrophilic monomer and then dispersing it in water.

The glass transition temperature (Tg) of the resin component of the film-forming vinyl resin emulsion that can be used in the present invention is 60°C or lower, preferably 40°C or lower. Also, is the solid content 5~? OX
The amount is 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. The emulsion contains Nissoside C8-12 (made of lead), butyl carpitol acetate, butyl cellosolve, carpitol, hexylene glycol, cellosolve, dibutyl glycol phthalate, sibutyl phthalate, pennol alcohol, diisopropyl succinic ester.

Pycal 94 (Atla3Chemical I
industries ) *Dalyad A (Do
A coating aid such as w-Chemical Cor) may be added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the solid content of the emulsion.

The non-film-forming emulsion (1) and the film-forming aqueous resin ■)
The mixing ratio of the former and the latter is usually 1 in solid weight ratio.
: 100-100:1, preferably 1:100-10
:1. When the solid content ratio of the non-film-forming resin emulsion (I) 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 has the effect of further improving the hiding property. The amount of titanium oxide to be blended is usually [solid content weight of above (1) + weight of titanium oxide]/solid content weight of above (II) = 1/100 to 100/1,
Preferably, 1/100 to 10/1 is appropriate.

Furthermore, all other paint additives can be incorporated into the composition of the present invention. Other additives for paint include heavy calcium carbonate, light calcium carbonate, kansuika, powder,
Kaolin, clay, calcined clay, Merck, silica sand, silica lime, bentonite, asbestos, pulp powder, white casten, ultrafine anhydrous silica, dolomite powder, magnesium carbonate, precipitated palicum sulfate, lithopone, zinc white, Fillers or pigments such as iron oxide, carbon black, chromium oxide, and ultramarine; phthalate esters such as dibutyl phthalate and dioctyl phthalate; aliphatic dibasic acid esters such as isodecyl succinate and zooctyl adipate; Phosphate esters such as cresyl phosphate, glycol esters such as diethylene glycol benzoate, epoxy plasticizers such as oxygenated soybean oil, chlorinated! Various plasticizers such as rough-ins, polyoxyethylene alkylphenyl ethers, and polybutene; Various anionic and nonionic surfactants; salts of butyric phosphoric acid such as pyrophosphoric acid, tripolyphosphoric acid, and hexametaphosphoric acid, and polycarboxylic acid. Dispersants such as acid salts and naphthalene sulfonates; Drying regulators such as mineral spirits and turpentine oil; Freeze or thaw stabilizing agents such as ethylene glycol, phlopylene gellicol, glycerin, and methanol; Antifoaming agents or preservatives Examples include. The amounts of these ingredients to be added are appropriately determined depending on the purpose.

Furthermore, in the case of a non-film-forming resin powder, it can be used not only in combination with the film-forming aqueous resin described above, but also in combination with an organic solution type film-forming polymer.

Such film-forming polymers are usually used for coatings or
If it is used for sealing materials, it can be used without any particular problem, but specific examples include vinyl copolymers, hydroxyl group-containing vinyl copolymers, alkyd resins, oil-free alkyd resins, and polyisocyanate resins. , blocked polyisocyanate resin, aminoplast, etc., and these can be used alone or as a mixture of two or more.

Specific examples of hydroxyl group-containing single crucibles include 2-hydroxyethyl (meth)acrylate, 2-hydroxyzolopyl (
meth)acrylate, 3-hydroxyzolopyl(meth)
Acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4
-Hydroxyalkyl esters of (meth)acrylic acid such as hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate; maleic anhydride, itacone anhydride Hydroxy alkyl ester monocardenic acids containing unsulfurized groups such as adducts of acid anhydride group-containing monomers such as Nami and glycols such as ethylene glycol; or polyhydric carbenoic acids such as maleic acid and fumaric acid → Examples include polyhydroxyalkyl esters containing an infm group, such as dihydroxyalkyl esters; and hydroxyalkyl vinyl ethers, such as hydroxyethyl vinyl ether.

Specific examples of other monomers that can be copolymerized with these include methyl (meth)acrylate, ethyl (meth)acrylate,
(meth)acrylic acid esters such as acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate; unsaturated, such as maleic acid, fumaric acid, itaconic acid Diesters of dicarnic acid and monohydric alcohol; vinyl acetate, vinyl benzoate,
Vinyl esters such as "Peova" (vinyl ester manufactured by Shell); "Viscoat 8F.

8FM, 3F, 3FMJ (fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth)acrylic V-), so-yp-fluorocyclohexyl fumarate, or N-1-telo Vinyl esters containing fluoroalkyl groups such as vinyl safe fluorooctane sulfonamide ethyl (meth)acrylate; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene Olefins such as styrene, α-methylstyrene, p-tart-butylstyrene, 〇-methyl-styrene, p-methyl-styrene and other aromatic vinyl monomers; (meth)acrylic acid, crotonic acid, maleic acid , fumaric acid, itaconic acid, or
A carboxyl group-containing monomer or radical such as citraconic acid? polycarboxylic acid anhydride group-containing unsaturated monomers such as maleic anhydride and itaconic anhydride 5: (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-alkoxymethylated (meth)acrylamide , soacetone acrylamide, N-methylol (meth)acrylamide, etc. Cardenamide group-containing monomers: p-styrenesulfonamide, N-methyl-
p-styrenesulfonamide, N,N-tumethyl-p-
Sulfonic acid amide group-containing monomers such as styrene sulfonamide; N,N-tumethylaminoethyl (
N,N-dialkylaminoalkyl (meth)acrylates such as meth)acrylates, or polyvalent carboxyl group-containing monomers such as maleic anhydride and polyvalent carboxylic acid anhydrides such as N,N-tumethylaminopropylamine. Tertiary amino group-containing monomers such as adducts with compounds having both an active hydrogen group and a tertiary amino group capable of reacting with the group; //ano group-containing monomers such as (meth)acrylonitrile: (meth)acrylic acid hydroxyalkyl ester has a phosphoric acid ester group obtained by a condensation reaction between a hydroquine alkyl ester of α, β-ethylenically unsaturated carboxylic acid and phosphoric acid or phosphoric esters. Monomers include monomers having a sulfonic acid group such as 2-acrylamido-2-methyl-propanesulfonic acid or organic amine salts thereof. The hydroxyl group-containing monomer to be copolymerized is used as necessary. In other words, (block), which will be described later,! ? Used in combination with lysocyanate resin and aminogellast. The amount of pattern polymer used varies depending on the molecular weight of the vinyl copolymer obtained, but is generally 5 to 30% of the total copolymer components. It is desirable that the monomer accounts for 95 to 70% by weight of the remaining 9. Other monomers can be freely selected. Such monomers should be determined taking into consideration other factors such as various physical properties of the cured product finally obtained and pigment dispersibility.

To obtain the above-mentioned hydroxyl group-containing vinyl polymer, any known method such as solution polymerization or solution pressure polymerization can be used, but solution radical polymerization is the simplest method. Typical solvents used in this case include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, i-frononol, n-butanol, and i-butanol. , m@C-butanol, alcohols such as ethylene glycol monoalkyl ether: vinegar s methyl,
Ester systems such as ethyl acetate and butyl acetate; acetone,
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and methyl amyl ketone, amide solvents such as dimethyl formamide and dimethyl acetamide, and mixtures thereof can be used.

Polymerization may be carried out by a conventional method using such a solvent and various polymerization initiators such as azo type or peroxidizing initiator.

Further, in this polymerization, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, and α-methylstyrene dimer can also be used as molecular weight regulators. In particular, when using 2-mercaptoethanol, which is a chain transfer agent containing hydroxyl groups, fraction F, which has a lower average molecular weight of the obtained polymer, has the drawback that it is difficult to efficiently introduce hydroxyl groups, resulting in poor weather resistance. , it is desirable to use it for limited purposes.

In addition to solution radical polymerization, there is also an ionic polymerization method as a method for producing the polymer, and polymers obtained by this polymerization method can also be used without any particular problems. According to this polymerization method, a monomer is polymerized using an ionic polymerization initiator whose functional groups have been blocked in advance, and the Zoroku agent at the end of the resulting polymer is eliminated, resulting in a polymer with an extremely narrow molecular weight distribution. A polymer always having one or more functional groups in one molecule is obtained.

As a specific method of such ionic polymerization method, for example, the method described in JP-A-58-13608 can be applied.

Z'+'/', ---1'~ Next, oil-free alkyd resin, as for alkyd resin, lice is 300 to 5. A material of the order of OOO is preferably used.

Specific examples of polybasic acid components used in synthesizing the polyester components of such alkyd resins and oil 7'-real alkyd resins include isophthalic acid, terephthalic acid, orthophthalic acid, and 2,6-naphthalene dicarboxylic acid. e
, 4,4'-diphenyldicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic Acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, superic acid, sepacic acid or dimeric fatty acid, cyclopentanetetracal? Also included are reactive derivatives such as phosphoric acid, trimellitic acid, pyromellitic acid, trimesic acid, and their alkyl esters and anhydrides.

These polybasic acids are appropriately used in consideration of the physical properties of the coating film, economic efficiency, and the like.

Next, as a specific example of the alcohol component used when synthesizing the polyester component.

Ethylene glycol, clopylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1.5--z-butanediol.

Alkylene glycols such as 1,6-hexaneol, neomethyl glycol, or 1,4-chlorohexanedimethanol, bishydroquine ethyl terephthalate, hydrogenated bisphenol A, or alkylene oxide adducts of bisphenol A :Aromatic glycols or alicyclic glycols can also be used as required, and it goes without saying that monoepoxy compounds can also be used in combination as glycol components. In addition, as trivalent or higher polyols, glycerin, trimethylolethane,
Trimethylolzolopane, pentaerythritol, cyintaerythritol, mannitol, and polyester compounds obtained by adding ε-caprolactone to the above-mentioned alcohol components can also be used.

Further, as described above, these alcohol components are also used as appropriate depending on the required performance of the final cured product.

Next, specific examples of fatty acids used when obtaining alkyd resin include octyl acid, palmitic acid, stearic acid, persatic acid, oleic acid, linoleic acid, liluic acid, coconut oil fatty acid, hydrogenated Coconut oil fatty acids, tall oil fatty acids, castor oil fatty acids, rice bran oil fatty acids, linseed oil fatty acids.

It is a long chain monobasic acid having 8 or more carbon atoms, such as soybean oil fatty acid, safflower oil fatty acid, or dehydrated castor oil fatty acid. These are selected in consideration of solubility in solvents, weather resistance of the coating film, economic efficiency, etc.

As described above, a vinyl copolymer, oil-free alkyd resin, and alkyd resin can be obtained. These may be used alone or as a mixture.

In addition to these, there are (block) polyisocyanate resins and aminoplasts, which react with the hydroxyl groups in the former three resins to give crosslinked cured products.

Specific examples of polyisonanate resins include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as quinrylene diisocyanate and isophorone diisocyanate; tolylene diisocyanate, 4.4'- Adducts of organic diisocyanates such as aromatic diisocyanates such as diphenylmethane diisonanate and polyhydric alcohols or low molecular weight polyester resins or water, or alternatively.

Specific examples of the isoneanate resin include organic diisocyanate and polyhydric alcohol or low molecular weight z; 7! ! Examples of typical commercially available products include IJ ester resin, adducts with water, etc., polymers of organic diisocyanates mentioned above, and iso7anate biuret.
-750,800゜DN-950,970'l or 1
5-455j (Inu Nippon Ink Chemical Industry Co., Ltd. product), “
Desmosier L, N, HL or ILj (West German Bayer out of stock), "Takene" D-102, 202
,ll0N,.

123NJ (product of Shikinichi Yakuhin Kogyo Co., Ltd.), ``Coronate L, HL, EH, or 203J (product of Nippon Polyurethane Industry Co., Ltd.), or ``Duuneto 24
Examples include A-90CX J (manufactured by Asahi Kasei Industries, Ltd.).

Next, as a specific example of the proc-isoanate resin, a polyisocyanate compound obtained by blocking the above-mentioned polyisocyanates using a known and commonly used blocking agent [Parnock D-550J (Inu Nippon Ink Chemical Co., Ltd. ) product), “Takene) B 815-N J (
Azoitol (AD)
DITOL) VXL-80J (manufactured by Hoechst Synthesis Co., Ltd.).

Next, aminoplast is melamine and urea.

Obtained by reacting an amine group-containing compound component such as acetoguanamine, benzoguanamine, steroguanamine, or spiroguanamine with an aldehyde compound component such as formaldehyde, laformaldehyde, acetaldehyde, or glyoxol by any known and conventional method. Any condensate or those obtained by etherifying these condensates with alcohol, etc., which are commonly used for paints, may be used. Of these, those partially or completely etherified with alcohols having 1 to 4 carbon atoms are preferred; specific examples of such aminoplasts include hexamethoxymethylmelamine, hexabutquinemethylmelamine,
Examples include metquin-butquin-methylmelamine, methoxymethylmelamine, butquin-methylmelamine, and condensates thereof.

The blending ratio of these (block) polyisocyanate resins and the former three hydroxyl group-containing vinyl copolymers, oil-free alkyd resins, and alkyd resins is determined by the effective incyanate groups in the (block) polyisocyanate resins and the former three. They are used by blending them so that the molar ratio of hydroxyl groups in the resin group falls within the range of 05 to 2.0. In addition, in the case of aminoplast, the solid content ratio is 10 to 40% by weight of aminoplast.

The former three resins are mixed in a proportion of 90 to 60% by weight.

The coating composition can produce a coating film with excellent weatherability, hiding properties, gloss, water resistance, etc. without adding any extender pigments.In particular, adding titanium oxide further promotes hiding properties and provides high coating properties. Can provide a glossy coating all over.

(Paper coating composition) The non-film-forming resin Emulnocon and its powder can be blended with a binder and an inorganic pigment to be used as a paper coating composition.

Binders used in the paper coating composition of the present invention include starch, oxidized starch, diconized starch, cationized starch, fused starch, acid-decomposed starch, modified starch such as dialdehyde starch, soybean protein, natural starch such as casein, etc. There are synthetic binders such as styrene-butadiene copolymer latex, calzequin-modified styrene-butadiene copolymer latex, polyvinyl acetate latex, and polyvinyl alcohol.

Among these binders, styrene-butadiene copolymer latex, especially acid monomer copolymerized amount of 0.5 to 10 weight layers? Kin-modified styrene-butatsuene copolymer latex and modified starch are preferred. Examples of acid monomers for the carbuquin-modified styrene-butanoene copolymer latex include unsaturated acids such as (meth)acrylic acid, itaconic acid, maleic acid, and fumaric acid.

Among styrene-butanoene copolymer latexes,
Butadiene component is 20 weight - 3% or more, preferably 25 to 3%
Those containing 50i★ are excellent in compatibility with inorganic pigments and non-film-forming resin emulsions or powdered products thereof, and in adhesion to coated paper. Furthermore, calgexi-modified styrene-butanoene copolymer, modified starch and fat
B type weight ratio of 0.01/1 to 99/1, preferably o
, It is suitable to use them together in a ratio of 1/1 to 10/1.

The ratio (A)/(B) of the bond combination (A) and the non-film-forming resin emulsion or its powder (B) is preferably 90 to 40/10 to 60. More preferably 80
~50/20~50. If the amount of (B) is less than 10 ml, the gloss and whiteness will be insufficient, and if the amount is more than 60 ml, the adhesive strength will tend to decrease.

Inorganic pigments that can be used in the present invention include kaolin clay, talc, barium sulfate, titanium oxide (lithyl, anatase), calcium carbonate, aluminum hydroxide, zinc oxide, satin white, and the like. Such an inorganic pigment has a ratio of inorganic pigment/non-film-forming resin emulsion or powdered product thereof.

It is preferable to use a dry weight in the range of 99.5 to 50/0.5 to 50 in terms of adhesive strength and other parameters ffJ.

The paper coating composition may contain other auxiliary agents such as dispersants (sodium birophosphate, sodium hexametaphosphate, sodium polycarbonate, etc.), antifoaming agents (sodium birophosphate, sodium hexametaphosphate, sodium polycarbonate, etc.) silicone oil) - Leveling agents (rot oil, non-andiamide, urea, etc.), preservatives, hydrating agents (formalin, hexamine, melamine resin, urea resin, glyoxal, zirconium ammonium carbonate, etc.), mold release agents ( Carunium stearate, rough-in emulsion), fluorescent dyes, colors, water retention improvers (carbyxymethylcellulose, sodium alginate, etc.) are added as necessary.

The method for applying the paper coating composition to the entire paper substrate is performed using known techniques.
For example, the coating may be performed using an air knife coater, a blade coater, a roll coater, or the like.

After coating, the surface is dried and finished by calendering, etc.

The composition for paper-like 1 is lightweight and has sufficient white discoloration.

Moreover, it has good adhesion performance and gloss performance, and since it has small pores, it does not inhibit the air permeability of the paper and can provide a film with good blister resistance. Accordingly, such paper coating compositions can be applied to paper to provide various coated products.

<! (Ii, Textile Treatment Composition) A non-film-forming resin emulsion and its powdered product can be added to a total adhesive and used as a textile treatment composition.

As the adhesive, a water-soluble resin or a polymer emulsion is used. Examples of such water-soluble resins include urea/formaldehyde or melamine/formaldehyde condensates, water-soluble polyesters, and polymer emulsions include acrylonitrile-butadiene rough latex.

Styrene-butadiene lac latex, chloroprene latex, polyvinyl chloride emulsion, polyacrylate emulsion, polyvinyl acetate emulsion,
In addition to Noyon, polyurethane emulsion, and the like, natural rubber latex and the like can be used, but are not particularly limited to these.

Processed fibers include cotton, natural fibers such as hemp,
Also, synthetic fibers such as rayon, recycled fibers, and artificial a! such as cellulose acetate. Synthetic fibers such as fiber, polyamide fiber, polyester fiber, acrylic fiber, polyolefin fiber, and polyurethane fiber may be used alone or in a mixed state. Such fibers are suitably in the form of webs, preferably non-woven fabrics.

The weight of the web is about 10 to 200 g per m2, preferably about 20 to 150 g per m2.

Approximately 30 g
A suitable range is from 60 to 100 weight by weight, preferably from about 30 to 60 weight by weight, based on the weight of the starting web.

In addition, the mixing ratio of the adhesive liquid used here, that is, the mixture of the adhesive and the non-film-forming resin emulsion or its powdered product, is 30 to 99.5 weight units of the former in terms of solid content;
Preferably, the weight ratio is 50-95, while the latter is 70-0.
It is preferably in the range of 50 to 5 weight.

The adhesive liquid may be used as an adhesive when manufacturing a normal nonwoven fabric, and the method of adhering the adhesive liquid to the web is not particularly limited.

That is, the adhesive may be applied by a wet method in which the web is immersed in the adhesive liquid of the present invention and wiped off, or it can be later dipped into a dry nonwoven fabric prepared by a needle punch method or a suf 4-send method. The adhesive liquid may be applied by a method such as a method, a spray method, a coating method, or the like.

Next, the obtained product is dried by heating at a temperature ranging from room temperature to 180° C. for 30 seconds to 60 minutes. Preferably 50℃
Force drying may be performed at ~150°C for 1 to 10 minutes.

The thus obtained nonwoven fabric has a soft texture,
It has no stickiness and has excellent properties such as strength of non-woven fabric, durability such as solvent resistance, and heat resistance, so it is suitable for use in clothing, sanitary materials, etc. It can be used for many purposes.

(Molding composition) A powdered non-film-forming resin emulsion can be mixed with all kinds of molding resins.

As the molding resin, polyprolene, f! IJ Polyolefins such as ethylene; FFA polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Non-foaming polyester resins: Polya J nide resins; Sulfur-containing resins such as Borifu-rensa-fido resin and polysulfone resin Resins; polyphenylene ether resins; polystyrenes; acrylonitrile-butadiene-styrene resins; vinyl chloride resins; epoxy resins; phenolic resins and the like can all be mentioned.

The mixing ratio of the molding resin and the powder is 100 parts resin.
0.01 to 1000 parts by weight.

Preferably, 0.1 to 500 parts by weight is appropriate.

An inorganic and/or organic filler can be added to the molding resin as necessary. Such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, no! Ilophyllite, bentonite, sericite.

Zeolite, mica, mica, nephelinnite, merk, atalpulgite, wollastonite.

PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz glass Can you name some reinforcing fillers such as? The resin also contains heat stabilizers, weather stabilizers, lubricants, and colorants.

Coupling agents, foaming agents, rust preventives, flame retardants, flame retardant aids such as antimony trioxide, etc. can all be added.

In addition, the molding composition can be used for various purposes depending on the resin it is wrapped in, and is particularly suitable for automobile inner bags (instrument quenelles, etc.) and exterior packaging (resin bumpers, etc.); industrial equipment such as ships: units. Household materials such as buses;
It is also useful for general household molded products and semiconductor encapsulation materials.

In addition to the above-mentioned uses, the non-film-forming resin emulsion and powdered product obtained in the present invention can be added to inks, adhesives, leather sealants, primers, abrasion resistance improvers for textiles, and the like.

〔Effect of the invention〕

The non-film-forming resin emulsion and its powdered product obtained in the present invention are excellent in weather resistance, gloss, hiding property, heat aging resistance, etc. In addition, UV absorbers are used to improve weather resistance.
It is also assumed that antioxidants mainly act to improve heat aging resistance.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, in which all parts and units 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, 2 parts of emulsifier (0.5 parts of Emuldan 920 manufactured by Kao Corporation, and itenol manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added. Add 1.5 parts of N-08) and maintain the internal temperature at 70°C.Hydroxyphenyl pensito+J azole UV absorber Tinuvin 328 (manufactured by Ciba Geigy)
2 parts to a mixture of 10 parts of styrene, 9.5 parts of methyl methacrylate, 0.25 parts of N-methylolacrylamide, 0.25 parts of acrylic acid, and 0.0 parts of ammonium persulfate.
A mixture of 5 parts of water and 4 parts of water was injected over about 1 hour to react, and the mixture was further aged for 1 hour. Thereafter, the internal temperature was kept at 70°C, and a mixture of 10 parts of Sanol 770 (manufactured by Ciba Geigy), a hindered amine ultraviolet absorber, 75 parts of styrene, 3 parts of methyl methacrylate, 4 parts of divinylbenzene, 0.25 parts of ammonium persulfate, and 5 parts of water. The mixture was injected for about 2 hours to react, and then aged for 45 minutes. After that, cool and add 25% ammonia aqueous solution.8.
Adjusted to 6. The resulting emulsion had a solid content concentration of 40
%, viscosity 15 cps (value at BM type rotational viscometer rotor AI, rotation speed 6 Orpm, temperature 25°C), -8,
6. Submicron particle analyzer (CoulteβN
-4) and an average particle diameter of 0.6 measured using an electron microscope.
μm, micro in particle? The diameter of the id was 0.25 μm.

This emulsion is designated as A-1.

Example 2 In a reaction vessel similar to Example 1, 100 parts of water and 2 emulsifiers were added.
(0 parts of Emuldan 9201 manufactured by Kao Corporation and 1.0 parts of Emal 20A manufactured by Kao Corporation) were added and stirred well. Next, the reaction vessel was kept at an internal temperature of 80°C, and 1.5 parts of G-SOAP 201 (Shiraishi Calcicum fi), a salicylic acid ester ultraviolet absorber, 5 parts of styrene, 10 parts of ethyl methacrylate, 0.5 parts of acrylonitrile, A mixture of 0.5 parts of ethylene glycol dimethacrylate, a mixture of 0.1 part of ammonium persulfate and 3 parts of water, and a mixture of 0.1 part of sodium monosulfite and 3 parts of water were each injected for about 1 hour to react. It was further aged for 1 hour. After that, the internal temperature was maintained at 70°C, and the zanoacrylate ultraviolet absorber Uvlsolater-300 (manufactured by Daide Kasei Co., Ltd.) 1 was used.
0 parts, 50 flfti of styrene, 3 p-methylstyrene
A mixture of 0 parts of ammonium persulfate and 4 parts of divinylbenzene; 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 injected over 2 hours and reacted at 70°C. Aging was carried out slowly for 45 minutes.

After that, cool it down and add 25% ammonia aqueous solution.
．． Adjusted to 4.

The obtained emulsion was designated as A-2, and its properties are shown in Table 1.

Example 3 In a reaction vessel similar to Example 2, 100 parts of water and 3 emulsifiers were added.
(1.5 parts of Emaldan 120 and Hite/Le N-0
A mixture of 0.1 part of potassium persulfate and 5 parts of water and the hindered bisphenol antioxidant Tsukuriday MS-6 (manufactured by Daien Shinko Kagaku Co., Ltd.) were added, keeping the internal temperature at 80°C. A mixture of 2.5 parts of methyl methallylate, 5 parts of ethyl acrylate, and 0.5 parts of γ-methacryloxyglobyltrimethoxysilane was injected over 1 hour to react, and the mixture was aged for 1 hour. Next, seasorb 2, a salicylic acid ester ultraviolet absorber, is added to the resulting emulsion.
03 (manufactured by Shiraishi Calcium Co., Ltd.) 10 parts, styrene 60 parts,
A mixture of 27 parts of α-methylstyrene and 2.5 parts of novinylbenzene and PI (adjusted with potassium persulfate) were used to obtain a fat-resistant emulsion.

The obtained emulsion was designated as A-3, and its properties are shown in Table 1.

Example 4 100 parts of water and 2 parts of emulsifier (1 part of Emuldan 120 and 1 part of Emal 20A) were added to the same reaction vessel as in Example 2, and the mixture was thoroughly stirred.

Next, the reaction vessel was kept at 80°C, and the hindered phenolic antioxidant Sumilide BHT (manufactured by Sumitomo Chemical Co., Ltd.) 2
．． 0 parts, 10 parts of methyl methacrylate, 5 parts of ethyl methacrylate, 1 part of divinylbenzene, 0.5 parts of acrylic acid
0.05 parts of ammonium persulfate and 4 parts of water
1 part of the mixture was injected in about 1 hour to react, and 1 part of the mixture
Time aged.

After that, the internal temperature was kept at 80℃ and the amine phenolic antioxidant 5uconox 4 (Summer Chemi
ca1) 10 parts, 70 parts of styrene, 10 parts of methyl methacrylate, 1 part of acrylic acid, 2 parts of divinylbenzene,
5 parts of the mixture and a mixture of 0.25 parts of ammonium persulfate and 5 parts of water were injected over about 2 hours to react, and the mixture was further aged for 45 minutes. Thereafter, it was cooled, and a 25% ammonia aqueous solution was added to adjust the temperature to 8.7.

The resulting emulsion was designated as A-4, and its properties are shown in Table 1.

Example 5 In the same manner as in Example 2, 100 parts of water and 2 parts of emulsifier (0.5 parts of Emuldan 920,) 1 Itenol N-0 were placed in a reaction vessel.
8) and kept the internal temperature at 70°C.
About 1 part each of a mixture of 10 parts of styrene, 4.5 parts of methyl methacrylate, 0.25 parts of glycidyl methacrylate, and 0.25 parts of acrylic acid, and a mixture of 0.1 part of ammonium persulfate and 3 parts of water The mixture was injected for an hour to react, and then aged for another hour. After that, the internal temperature was maintained at 70℃, and the aromatic amine antioxidant Tenamen@5 was added.
(manufactured by Eastman Chemical Company) 10 parts, 55 styrene
A mixture of 25 parts of p-methylstyrene, 5 parts of ethylene glycol dimethacrylate, and a mixture of 0.2 parts of ammonium persulfate and 5 parts of water were each injected over a period of 2 hours.
The reaction was carried out at 0°C and aged for 45 minutes.

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

Examples 6 to 10 Each resin emulsion A-6 to 9 was prepared in exactly the same manner as in Examples 1 to 5, except that the ultraviolet absorber and 10R antioxidant were blended and polymerized as shown in Table 1. I got it.

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 an emulsifier (same as in Example 1) were added to a reaction vessel similar to that in Example 1, and the mixture was thoroughly stirred.

Next, heat the reaction vessel and maintain the internal temperature at 70℃ using styrene 1
0 parts of methyl methacrylate, 0.25 parts of N-methylolacrylamide and 0.25 parts of acrylic acid, and a mixture of 0.05 parts of ammonium persulfate and 4 parts of water were injected over about 1 hour to react. It was further aged for 1 hour. Afterwards, the internal temperature was maintained at 70°C, and a mixture of 75 parts of styrene, 3 parts of methyl methacrylate, and 2 parts of divinylbenzene, and a mixture of 0.25 parts of ammonium persulfate and 5 parts of water were injected over about 2 hours, and the mixture was aged for 1 hour. did. After that, cool the resin emul-7w7A'-1 by adjusting the pH.
Ta. Table 1 shows the properties of this emulsion.

Comparative Example 2 3282 parts of Tinuvin, 10 parts of Sanol 770 and 50r of tetrahydrofuran! L! ! Resin emulsion A'-2 was obtained by blending the resin emulsion A'-1 with the above emulsion A'-1 at a solid content weight ratio of 12:100. The properties of the resin emulsion A'-2 are shown in Table IVC.

Comparative Example 3 A resin emulsion was obtained in exactly the same manner as in Example 1, except that the first-stage reaction and second-stage reaction were performed in reverse. Table 1 shows the properties of this emulsion.

Comparative Example 4 In a reaction vessel similar to Example 1, 100 parts of water and 2 emulsifiers were added.
(same as in Example 1) and stirred well. Next, heat the reaction vessel and keep the internal temperature at 70℃,
82 parts, 77010 parts of Sanol, 85 parts of styrene, 12 parts of methyl methacrylate, 2 parts of divinylbenzene,
A mixture of 0:25 parts of N-methylolacrylamide, 0.25 parts of acrylic acid, and 0.3 parts of ammonium persulfate.
A mixture of 5 parts and 5 parts of water was injected over a period of about 3 hours, and the mixture was heated for 1 hour. Thereafter, it was cooled and one adjustment was made to obtain resin emulsion A'-3. The properties of this emulsion are shown in Table 1.

Comparative Example 5 A resin emulsion was obtained in exactly the same manner as in Comparative Example 1, except that the first-stage reaction and second-stage reaction were performed in reverse. Table 1 shows the properties of this emulsion.

Add 2 parts of a curing agent (same as in Example 5), stir well, and combine the ultraviolet absorber, antioxidant, monomer, and initiator solutions used in Example 5 in about 3 hours using the 90 method. The mixture was further aged for 1 hour and then cooled to obtain an emulsion. Table 1 shows the properties of this emulsion.

1) Phase Qh composition; C...acrylonitrile, n-BA...n-butyl acrylate, S...
Styrene, N-M) J, 1...N-methylolacrylamide, MMA...methacrylic acid, AA...acrylic acid, t-BMA...t-butyl methacrylate, ω Buddha...glycidyl methacrylate , EGDM...ethylene glycol dimethacrylate, p-MSt...p
-Methylstyrene, gA...ethyl acrylate, E
MA...Ethyl methacrylate, α-MSt...
α-methylstyrene, KBM-503...γ-methacryloxyglobyl trimethoxy 7ran (Shin-Etsu Chemical ■), DVB...novinylbenzene 2) Contact angle: 1st stage copolymer polymer Contact angle of water droplets on the solid surface D2: Contact angle of water droplets on the solid surface of the second-stage copolymer polymer Measurement of contact angle: The contact angle of water droplets on the polymer solid surface is calculated using the Tsukiermagoniometer method based on the vector of the energy component below. Measured by a contact angle measuring device γW: Surface tension of water dyne α-1 γ,: Optical surface free energy of solid erg cmγ: Interfacial free W energy between solid surface and water 3) D2-D,: Second stage Difference in the contact angle of water droplets on the polymer solid surface between the copolymer polymer and the first stage copolymer polymer 4) Glass transition temperature (ridge value) of the entire polymer composition 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 and A'-2 of Comparative Examples 3 to 5
16.1 parts of each resin emulsion of 3 to A'-5, acrylic-styrene copolymer tB as a film-forming resin emulsion
Jk emulsion (VONC manufactured by Inu Nippon Ink Chemical Industry)
60.1 parts of OAT Ec-880) and 71 parts of an aqueous dispersion of rutile titanium dioxide were blended as shown in Table 2,
To the mixture were slowly added 1.4 parts of tributyl phosphate, 16.5 parts of water, and 0.18 parts of hydroxy-7-ethyl homeolulose, and the mixture was stirred until the viscosity became constant.

The resulting paints were applied side by side on a Morest hiding power chart to form a film of the same thickness and air-dried for 3 days. Table 2 shows the physicochemical properties of these coatings.

7.7' Test conditions 1) Particle size: ■ Measured from a scanning electron micrograph of the emulsion ■ Measured using a submicron particle analyzer (Coultsr mode I N-4) 2) Mechanical stability: -1-? Load 1 ok x 3,000rpr using Luzo-N 501i' Omaron testing machine
The amount of aggregate formed after treatment with n for 10 minutes was measured and calculated using the following formula.

Δ... (4) is 0.5 coefficient or more 3) Polymer solubility: Tochi resin howder after water evaporation of the emulsion was added to each solvent and observed (11 degrees and 5 degrees).

(1) 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 at 23°C and 651 RH. After drying for 1 day, it was measured at 90'10' using a Murakami gloss meter.

5) Gloss (Glass plate) 2. 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.

6) Gloss After the prepared paint was left for one day, it was applied to hidden (hidden rate EM) coverage test paper using a 6 mil applicator, and after drying for 5 days at 23℃ and 65℃RH, Murakami gloss was obtained. Measured with a meter.

7) Measure the gloss at 45° 10° of the coating film with opacity = 6) on the black and white areas of opacity test paper (manufactured by Japan Test Panel Industry ■), and calculate the ratio 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) O: No swelling, 1 part of pristalling Δ
... Swollen fabric, 〃 ×... Swelling dog, a lot of pristaring 9) After the water resistance test: After the test in 8), the gloss of the coating film was measured using a Murakami gloss retention rate gloss meter, 5 ) is expressed as a percentage of gloss.

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

(Evaluation) O... Swelling cloth, no pristaring ×...
・Swelling fabric, with blistering 11) Alkali resistance test: 0 gloss retention after coating after the alkali resistance test in 10) Dry at room temperature for 2 days to reduce gloss (60°/60') t
12) Washing resistance: Paint was applied to a matte PVC sheet with a 6 mil applicator and after drying for 7 days, measured using a Gardner washing resistance tester.

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

6.12. Visually judge the condition after 24 months of exposure.

(Upper row = 6 months later, Middle row = 12 months later, Lower row = 24 months later) (n) ○...Good Δ...Normal Test the board coating after drying it for 7 days.

(Test conditions) Sunshine Wederometer upper stage
Lower row after 500 hours After 1000 hours (evaluation) O...good Δ...fair
0 and A'-2 to 5, 16.1 parts of each aqueous 7-chlorostyrene emulsion (using VONCOAT 5460, manufactured by Inu Nippon Ia dP Chemical Industry) 60
71 parts and 16.5 parts of aqueous dispersion of rutile titanium dioxide
Added 8 parts. Tributyl phosphate L 4 parts, water 16.
5 parts of hydroxyethylcellulose and 0.18 parts of hydroxyethylcellulose were added slowly and the mixture was stirred until its viscosity was constant. The various paints mentioned above (morest)
Apply it side by side on the concealment chart and on the glass plate,
A coating film of the same thickness was formed 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 yen, PVC is 27.3 volume i%, and mouse is 39
．． 4%.

Examples 11 to 16 A-1, A-2, A-3, A-4 synthesized in the above actual case
, A-5, and A-6, each emulsion of 5.6 μm was dried in a spray dryer (Mobil Minor type for small research and development, Ashidewa Nitro Atomide @) at a p inlet temperature of 150 ~
200°C and dropping rate 2. A resin powder was obtained in 3 hours under the condition of O1/hr.

Table 4 shows the characteristics of each resin powder obtained.

a″″ Note) / Remer solubility 0 indicates dull fraction (→).

Note) 1) Particle size: Measured by scanning electron micrograph of fine powder 2) Thermal decomposition temperature: Measured by differential thermal analysis in N2 3) Polymer solubility: 1 g of fine powder was washed 3 times with lOd of each solvent. (
Centrifugal 1 hr) After residual powder weight (calculate the I remargin fraction using the following formula) - (Residual powder type! 7 / Gokiji, Kuyag →
X 100MIBK: Methyl isobutyl ketone Application example 3 7.7 parts of each resin powder obtained in Examples 11 to 16, acrylic-styrene resin emulsion (Dainippon Ink & Chemicals)
60.1 parts of VONCOAT EC-880) and 16.6 parts of a 71% aqueous dispersion of rutile titanium dioxide, and to the mixture were added 1.4 parts of tributyl phosphate and 2 parts of water.
4.9 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 morsat (morsat) hiding power chart to form a uniformly thick film and air-dried for 3 days. Table 5 shows the physicochemical properties of these coatings.

Application example 4 Adhesive VONCOAT R3119 (non-volatile content: 45 cm, Tg knee 15°C, manufactured by Dainippon Ink and Chemicals (hereinafter referred to as R)
-1) 100 parts, vONCOATv (non-volatile content:
29%, pH 2.5, Dainippon Ink & Chemicals Co., Ltd.) and A-1 of Example 1, A-1 of Example 60A-6, and A'- of Comparative Example 1.
1. Mix A'-2 of Comparative Example 2 and resin emulsions A'-3 to 5 of Comparative Examples 3 to 5 according to the formulation shown in Table 6, and further dilute with water to make the solid content 30%. An adhesive liquid was obtained.

Next, the above adhesive solution was applied to a resin web having a weight of 1509/m2 and made of 60 pcs of polyester fibers of 3.0 denier/51 m and 40 pcs of rayon fibers of 3.0 denier 151W111. The impregnation name is determined so that the mold ratio is approximately 1:0.6.

Next, it was dried in a hot air circulation dryer under the drying conditions shown in Table 6 to obtain a nonwoven fabric. The physical properties of the obtained nonwoven fabric are also shown in Table 6.

Test method〉 Weight (17m2): Thickness according to JfS-L-1085 ■)°〃 5% modulus (kg15 side): 7 Strength (Y75cm) Dry cleaning resistance 20 Good, × Bad drag resistance ゛○Good, ×Fumachi yellowing resistance:
Heat resistance 14 (FX24HR8○ Good, × Not good As shown in Table 6, the nonwoven fabric made of adhesive containing the ultraviolet absorber-filled hollow resin particle emulsion of the present invention has little deterioration in light resistance, sufficient flexibility, and Dry cleaning resistance,
It has good drapability performance.

Application example 5 A-1 of Example 1, A-6 of Example 6, AI of Comparative example 1
-1 and A'-2 of Comparative Example 2, each resin emulsion and binder (carboxy-modified styrene-butatsuene copolymer latex powder and oxidized starch) and inorganic pigments (clay and calcium carbonate) are blended in the following proportions. Then, coated paper was produced using this.

Table 7 shows the evaluation results for the coated paper.

(Blend of paper coating composition) Clay (Mineral Chemical Filigs fiVW-90
) 90 parts calcium carbonate (PZ manufactured by Shiraishi Kogyo ■
) 10 parts oxidized starch (egg cornstarch■
Oji Ace B) 6-part non-film-forming polymer particles Variable Calbuquin modified Silsig b
Hin Copolymer Futetsutabe A) 10 parts Each application test was conducted as follows.

Whiteness: Measured using Hunter colorimetry and a whiteness meter.

White paper gloss: using a Murakami gloss meter at an incident angle of 75°.

Measure at a reflection angle of 75°.

Dry adhesion strength (RT): Printed 15 times with rprφ6 ink using a scatter type RI printability tester, and evaluated using a 5-point method, with no picking being scored as 5.

Water resistant adhesion strength (WP): Using R1 printing suitability tester τ type, apply water with IPTφ4 ink, print, reverse, and judge using a 5-point method with picking as 1 and fc and no picking as 5. .

Light resistance: Fade meter (85℃ light source, Be JV-Ca
rbon-Arc) for each specimen at 100HR8, 30
Measuring the numerical values of various applied tests after 0HR8 irradiation.

From the evaluation results in Table 7, in Examples A I and 2 of the present invention, white paper gloss, whiteness, dry adhesive strength, and water-resistant adhesive strength are all maintained at a certain level or higher in a well-balanced manner. Moreover, the rate of decline in each part after the light resistance test is extremely small. On the other hand, the hollow resin particles (comparative example A3) containing the ultraviolet absorber an dlor and the antioxidant are well balanced, and the rate of decrease in each component after the light fastness test is slightly larger. In the case of a blend (Comparative Example A4), it is difficult to disperse and the effect of the ultraviolet absorber is short lasting. The homogeneous copolymer (Comparative Nichiya 5) has a small particle size and is therefore unbalanced in terms of whiteness, etc.

Application example 6 30 parts of the resin powder obtained in Example 11 and commercially available polypropylene resin J-709HK (Ube Industries ■ product)
, Granac B, a polybutylene terephthalate resin
T-1000 (Dainippon Ink & Chemicals @Product), Dick PPS FZ, a polyphenylene sulfide resin
-1140 (Dainippon Ink Chemical Industry ■ product) and 70 parts of each were kneaded to prepare test pieces under the conditions shown in Table 8.

The obtained test pieces were exposed to the accelerated weathering test shown in Table 8 to evaluate their weather resistance. The results are shown in Table 8.

Procedure Amendment Written May 7, 1986 Michibu Uga, Commissioner of the Patent Office Indication of the Tonori Case 1985 Patent Application No. 233550 2 Title of Invention Process for producing non-film-forming resin emulsion for use other than cosmetics and its relation to the powdering method 3 and the case of the person making the amendment Patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2)
88) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Tel: Tokyo (03) 272-4511 C, Representative) (
8876) Patent Attorney Katsutoshi Takahashi 5, Column 6 of Detailed Description of the Invention of the Specification Subject to Amendment, Contents of the Amendment (1) "Polymerizable Monomer" in Line 4, Page 10 of the Specification Corrected to "quantity".

(2) "N,N'-di-β-naphthyl-p-7enyldiamine" in lines 6 to 5 from the bottom of page 13 of the circular is replaced with rN,N-
Corrected to "No β-naphthyl-p-phenylenediamine."

(3) In the same book, page 14, line 13, r
Zinc N,N'-tumethyldithiocarbamate".

(4) Same book, page 14, line 15 Correct "thiopro" to "thiodizoro".

(5) "2-mercaptoethanol" in the bottom line of page 34 of the same book is corrected to "2-mercaptoethanol."

(6) Same book, page 42, line 13 Correct "divalent starch" to "pregelatinized starch".

(7) Change “90-40/10-60” from the bottom line of page 43 of the same book to “95-2.5/5”
Corrected to ~97.5 J.

(8) "~5'O/20~50J" in the first line of page 44 of the same book is corrected to "~5/20~95."

(9) Same book, page 44, line 1 "Correct 10% by weight to 5% by weight."

(ILO Ministry of Finance, page 44, lines 2-3) Correct "60 weight i%" to "r　97.5 weight%".

α■ Same book, page 48, line 14 Correct "polyprolene" to "polypropylene".

(6) "Cyanoacrylate" on page 53, line 6 of the same book has been corrected to "cyanoacrylate."

(To) "Ethyl acrylate" on page 54, line 4 of the same book is corrected to "ethyl methacrylate."

α◆ Table 1 on page 60 of the same document is corrected as shown in the attached sheet.

(G) Same book, page 62, line 4 Correct "Kobutsu" to "MAA J."

αQ Same book, page 72, line 5, ``Nitroatomyde'' is corrected to ``Niroatomyde''.

u'f) In the same book, page 77, line 5, change "Intensity (kfi + 15 tan)" to "Intensity (yu 15 cns)".
: Corrected to tJ.

Correct "balanced and after the light test" in line 7 of page 82 of the α God Dosho to "balanced but after the light test" - Above procedural amendment September 1985 IQI Japan Patent Office Commissioner Black 1) Mr. Akio 1, Indication of the case, Patent Application No. 233550 of 1985, 2, Name of the invention, Process for producing non-film-forming resin emulsion used for purposes other than cosmetics, and its powderization method 3, Person making amendment, and Relationship Patent applicant address: 35-58 Sakashita, Itabashi-ku, Tokyo (288
) Inu Nippon Ink Chemical Industry Co., Ltd.
Kuni Mura Shigeru 4, Agent: Dainippon Ink and Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone: Tokyo (03) 272-4511 (main representative) (887)
6. Katsutoshi Takahashi, a specialist in the field of detailed description of the invention, section 7. Contents of amendment (1) The statement on page 21, line 8 is corrected as follows.

"It evaporates during drying. Also, non-film-forming vinyl resin particles are resins with a glass transition temperature of 40°C or higher, preferably 50°C or higher, and ultraviolet absorbers and/or antioxidants are encapsulated in the resin. The UV absorber and/or
or the antioxidant is physically fixed,
Moreover, it refers to so-called non-film-forming resin particles that do not have film-forming ability at room temperature, and usually "(
2) “Table 1” on page 60 is corrected as follows.

Claims (1)

[Claims] 1. An emulsion polymer emulsion which may contain an ultraviolet absorber and/or an antioxidant is added with a polymer having a water contact angle 1 to 110° higher than that of the polymer in the emulsion. 1. A method for producing a non-film-forming resin emulsion for use in products other than cosmetics, which comprises adding at least one type of radically polymerizable monomer, a UV absorber and/or an antioxidant, and carrying out emulsion polymerization. 2. At least one species capable of forming a polymer having a water contact angle 1 to 110° higher than that of the polymer of the emulsion, in the emulsion polymer emulsion which may contain an ultraviolet absorber and/or an antioxidant. A method for powdering a non-film-forming resin emulsion for use in products other than cosmetics, which comprises adding a radically polymerizable monomer, an ultraviolet absorber, and/or an antioxidant, emulsion polymerization, and then powdering.