JPH09157495A - Emulsion curable with active energy ray and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion curable with active energy rays excellent in dispersion stability and giving cured film excellent in resistance to water and solvent by introducing a compound curable with activated energy rays into the emulsion particles. SOLUTION: (A) Emulsion particles are allowed to include (B) a compound curable with active energy rays. In the case that the emulsion is cured with ultraviolet rays, (C) a compound curable with ultraviolet rays and (D) a photopolymerization initiator are preferably used as the component B. The component A is preferably three-dimensionally cross-linked and is for example, a polymer emulsion prepared by reaction of a cross-linkable vinyl monomer, a vinyl monomer and a polymerizable emulsifier. The objective emulsion is produced by emulsifying the component B or component C and component D in water and mixing them with component A so that the component B or C and the component D are included in the component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray curable emulsion and a method for producing the same. The active energy ray-curable emulsion of the present invention can be used for various applications in which an active energy ray-curable compound or a composition thereof has been conventionally used, for example, applications such as paints, printing inks, surface coating materials and photoresists. .

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable compounds have been used in a wide variety of fields for the purpose of solving environmental problems such as odor, improving productivity and simplifying equipment. However, active energy ray-curable compounds often have to be used in combination with a relatively low molecular weight polymerizable diluent or an organic solvent due to their handling problems and coating requirements. It has problems of skin irritation, toxicity, odor, flammability, etc.

For the purpose of solving these problems, a method of introducing a hydrophilic site into an active energy ray-curable compound by copolymerization or the like to impart self-water dispersibility or self-emulsification property, a conventional active energy ray-curable compound By a method of dispersing or emulsifying using a low-molecular type or high-molecular type emulsifier, and further by a method of using an active energy ray-curable compound dispersed or emulsified by the above method and an acrylic emulsion or a water-soluble polymer. Various types of water-soluble active energy ray-curable compounds and active energy ray-curable emulsions have been developed. But,
Emulsions and the like obtained by these methods have insufficient dispersion stability, and problems such as water resistance, solvent resistance, weather resistance and mechanical properties (eg hardness) of the cured film remain.
The current situation is that it has not yet been put to practical use.

Further, JP-A-2-300204 and JP-A-4-294353 disclose a method for producing an emulsion in which a polymerizable double bond is introduced on the particle surface. Such an emulsion can prevent problems of dispersion stability and deterioration of water resistance and weather resistance of the cured film,
In particular, the emulsion of crosslinkable particles having polymerizability is
Since the crosslink density can be increased, it is also very effective in applications in which the water resistance and weather resistance of the cured film are required. However, the manufacturing methods described in these publications have a problem that the range of product design is limited, the manufacturing process is complicated, and the cost is increased.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an emulsion having active energy ray curability, dispersion stability and film-forming property, which can be produced by a relatively simple method.
Moreover, it is an object of the present invention to provide a cured product excellent in water resistance, solvent resistance, weather resistance, mechanical properties and the like.

[0006]

In view of the above situation, the present inventor has conducted extensive studies to solve the above problems. As a result, the emulsion particles approach, adhere, and coalesce with each other as water evaporates during the drying process to form a film. Therefore, if the composition, Tg, crosslink density, etc. of the emulsion particles are adjusted, the interparticles We paid attention to the fact that particles can be fused to the extent that mass transfer is possible. Then, by introducing an active energy ray-curable compound inside the emulsion particles, it is possible to obtain a novel active energy ray-curable emulsion having good dispersion stability that gives a cured film excellent in water resistance, solvent resistance and the like, Furthermore, by using three-dimensionally crosslinked emulsion particles for introducing the active energy ray-curable compound, it is possible to dramatically increase the crosslinking density of the final cured film, and to improve the solvent resistance of the cured film. The inventors have also found that weather resistance and the like can be greatly improved, and have completed the present invention.

That is, according to the present invention, an active energy ray curable emulsion containing an active energy ray curable compound inside an emulsion particle, and an ultraviolet ray curable compound and a photopolymerization initiator inside an emulsion particle are contained. The present invention relates to an active energy ray-curable emulsion, and further relates to a method for producing these active energy ray-curable emulsions.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, emulsion particles into which an active energy ray-curable compound is introduced can be produced by emulsion polymerization of various vinyl monomers in the presence of an emulsifier.

Examples of the vinyl monomer include aromatic monovinyl compounds such as styrene, α-methylstyrene, fluorostyrene and vinylpyridine; methyl (meth).
Acrylate {Note that (meth) acrylate means acrylate or methacrylate. Below (meta)
And have the same meaning. }, Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, glycidyl (meth) acrylate, N,
(Meth) acrylic acid ester monomers such as N-dimethylaminoethyl (meth) acrylate; vinyl cyanide compounds such as (meth) acrylonitrile; mono- or dicarboxylic acids or dicarboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid Acid anhydrides; amide-based monomers such as (meth) acrylamide; and ionic monomers such as sodium styrenesulfonate and sulfonated isoprene. In addition, conjugated double bond compounds such as butadiene and isoprene, vinyl esters such as vinyl acetate and α-olefins such as 4-methyl-1-pentene are also acceptable within a range which is allowable in terms of polymerization rate and stability during polymerization. Can be used.
These vinyl monomers may be used alone or in combination of two or more.

When it is desired to three-dimensionally crosslink the emulsion particles to increase the crosslink density, a crosslinkable vinyl monomer can be used. Examples of crosslinkable vinyl monomers are divinylbenzene and ethylene glycol di (meth).
Acrylate, 1,3-butylene glycol di (meth)
Examples thereof include acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol (meth) acrylate, and methylenebisacrylamide. In the present invention, among these crosslinkable vinyl monomers, divinylbenzene and ethylene glycol dimethacrylate are particularly preferable. These crosslinkable vinyl monomers may be used alone or in combination of two or more. These crosslinkable vinyl monomers are used as a mixture with the above-mentioned monofunctional vinyl monomer, and the amount thereof is 20 mol% or less, preferably 0.1 to 20 mol%, more preferably 0, based on the total amount of vinyl monomers. .5-1
0 mol%. The amount of crosslinkable vinyl monomer used is 20
If it exceeds%, it becomes difficult to introduce the active energy ray-curable compound, which is not preferable.

As the emulsifier, those used in ordinary emulsion polymerization can be used. For example, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dialkylsulfosuccinate, formalin condensate of naphthalene sulfonic acid, anionic emulsifiers such as polyoxyethylene alkylphenyl ether sulfate ammonium salt, polyoxyethylene nonylphenyl ether, polyethylene glycol Examples thereof include nonionic emulsifiers such as monostearate and sorbitan monostearate.

As the emulsifier, a polymerizable emulsifier can be used in combination with the anionic emulsifier, the nonionic emulsifier, or the like, or alone. The polymerizable emulsifier is, for example, (meth) allyl group, 1-propenyl group,
An emulsifier having at least one polymerizable functional group in its molecule, such as a 2-methyl-1-propenyl group, a vinyl group, an isopropenyl group, a (meth) acryloyl group. Among these, a polymerizable emulsifier having a (meth) acryloyl group as a polymerizable functional group is preferable. Specifically, a sulfosuccinic acid ester salt of polyoxyethylene alkyl ether having the functional group in the molecule, a sulfuric ester ester salt of polyoxyethylene alkyl ether having the functional group in the molecule, a polyoxyethylene alkyl ether having the functional group in the molecule Examples thereof include sulfosuccinic acid ester salts of oxyethylene alkyl phenyl ethers and sulfuric acid ester salts of polyoxyethylene alkyl phenyl ethers having the above-mentioned functional group in the molecule. Furthermore, an acidic phosphoric acid (meth) acrylic acid ester-based emulsifier having the functional group in the molecule, a phosphoric acid ester of an oligoester (meth) acrylate having the functional group in the molecule or an alkali salt thereof, and the functional group in the molecule Examples thereof include oligoester poly (meth) acrylates of polyalkylene glycol derivatives having a hydrophilic alkylene oxide group contained therein. Furthermore, a neutralized product of a (meth) acrylic copolymer having a tertiary amino group may be added with a compound having an epoxy group such as grididyl (meth) acrylate and an α, β-unsaturated double bond. It is also possible to use a polymer-type polymerizable emulsifier obtained by the method.

Since the polymerizable emulsifier is copolymerized with the vinyl monomer and incorporated into the emulsion particles, it is possible to eliminate the free emulsifier which causes foaming of the obtained emulsion and deterioration of water resistance of the cured film. Therefore, in the present invention, it is preferable to use a polymerizable emulsifier as the emulsifier. Further, among the polymerizable emulsifiers, those having at least two polymerizable functional groups in the molecule can increase the crosslink density of emulsion particles without using a crosslinkable vinyl monomer. It goes without saying that a crosslinkable vinyl monomer can be used when producing emulsion particles having a higher crosslink density. The polymerizable emulsifier having two or more polymerizable functional groups in the molecule may be a mixture containing a polymerizable emulsifier having one polymerizable functional group.

Commercially available products of the polymerizable emulsifier having two or more polymerizable functional groups in the molecule are (trade name: KAYAM).
ER PM-2, manufactured by Nippon Kayaku Co., Ltd., (trade name: New Frontier A-229E, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
(Trade name: New Frontier N-250Z, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like can be given as typical examples. Also,
Examples of the polymerizable emulsifier having one polymerizable functional group in the molecule include JP-A-63-23725 and JP-A-63-24.
No. 0931, JP-A-62-104802, (trade name KAYAMER PM-1, manufactured by Nippon Kayaku Co., Ltd.), (trade name SE-10N, manufactured by Asahi Denka Co., Ltd.) , (Brand name NE-10, Asahi Denka Co., Ltd.
Manufactured by Asahi Denka Kogyo Co., Ltd.,
(Brand name NE-30, manufactured by Asahi Denka Kogyo Co., Ltd.), (Brand name New Frontier N-117E, Dai-ichi Kogyo Seiyaku Co., Ltd.)
(Product name), (Product name Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), (Product name Aqualon HS-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), (Product name Eminor JS-2, Sanyo Kasei ( Co., Ltd.), (trade name: Latemur S-120, manufactured by Kao Corporation), (trade name: Latemur S-180, Kao Corporation)
Commercially available products such as manufactured products are typical examples.

The type of emulsifier can be set in consideration of the particle size, stability, crosslink density and physical properties of the cured film of the obtained emulsion particles. The amount of the emulsifier used is usually about 0.1 to 80% by weight, preferably 5 to 50% by weight, based on the total amount of the vinyl monomer. In the case of producing emulsion particles having an average particle diameter of 100 nm or less, it is preferable to use the emulsifier in an amount of 5% by weight or more because the dispersion stability of the emulsion particles deteriorates.

The temperature of emulsion polymerization is about 50 to 95 ° C, preferably 65 to 85 ° C. The concentration at the time of emulsion polymerization is such that the solid content of the vinyl monomer and the emulsifier is about 10 to 50% by weight, preferably 15 to 40% by weight.

Further, the polymerization initiator used in the emulsion polymerization is not particularly limited as long as it is one that is usually used in the emulsion polymerization. For example, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, organic peroxides, water-soluble radical polymerization initiators such as aqueous azo initiators, etc., alone or in combination with the above-mentioned peroxides. It is possible to use a redox type polymerization initiator in which a sulfate or the like is combined with various reducing agents such as sodium hydrogen sulfite, sodium thiosulfate, and ascorbic acid. The amount of the polymerization initiator used is
It is preferably in the range of 0.005 to 5 mol% with respect to the total amount of vinyl monomers. Further, in the case of producing fine crosslinked emulsion particles having an average particle size of 100 nm or less using a polymerizable emulsifier, it is preferable to use a redox catalyst in the presence of a transition metal ion such as divalent copper ion. . The transition metal ion concentration in the reaction system is usually 1.0 x 1
It is preferably about 0 ^{−8 to} 1.0 × 10 ⁻³ mol / liter.

Emulsion particles having an average particle size of about 0.05 to 500 μm into which the active energy ray-curable compound can be introduced can be obtained by the emulsion polymerization described above.

The active energy ray-curable emulsion of the present invention contains an active energy ray-curable compound inside the emulsion particles.

As the active energy ray-curable compound,
The following prepolymers and monomers are listed. As the active energy ray-curable prepolymer, epoxy (meth) acrylate, polyurethane (meth) acrylate, polyethylene (meth) acrylate, polyether (meth) acrylate, silicone (meth) acrylate, polybutadiene (meth) acrylate, polyamide (meth ) Acrylate etc. can be illustrated. Further, as the active energy ray-curable monomer, vinyl monomers such as styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-
Hexyl acrylate, cyclohexyl acrylate,
Monofunctional monomers such as n-dodecyl acrylate, isophoronyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, bisphenol A diethoxydiacrylate, trimethylolpropane triacrylate, Examples thereof include polyfunctional monomers such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. The amount of these active energy ray-curable compounds used is usually 2 with respect to the total solid components of the emulsion particles.
It is in the range of about 0 to 500% by weight, preferably 50 to 200% by weight.

When the active energy ray-curable emulsion of the present invention is cured by ultraviolet rays, a photopolymerization initiator is introduced into the emulsion particles together with the active energy ray-curable compound. On the other hand, when curing with an electron beam, a photopolymerization initiator is unnecessary. As the photopolymerization initiator, those usually used for curing an ultraviolet curable compound can be used. For example, acetophenone, benzophenone, benzoin ether, chloroacetophenone, diethoxyacetophenone, α-aminoacetophenone, benzylmethyl ketal, thioxanthone, α-acyl oxime ester, acylphosphine oxide, glyoxy ester, 3-ketocoumarin, 2-
Examples thereof include ethyl anthraquinone, camphor quinone, Michler's ketone and the like. These photopolymerization initiators are usually used in the range of about 0.1 to 10% by weight with respect to the active energy ray-curable compound (ultraviolet curable compound) introduced into the emulsion particles.

In the present invention, the active energy ray-curable compound (or the ultraviolet ray-curable compound and the photopolymerization initiator) is referred to in the emulsion particles. Hereinafter, when the active energy ray-curable compound is the ultraviolet ray-curable compound, photopolymerization is performed. The method used in seed polymerization can be applied as a method of introducing the initiator). That is, in seed polymerization, which is being studied in various fields as a method for controlling morphology according to the application of emulsion products such as core / shell structure and a method for synthesizing porous, irregularly shaped and hollow fine particles, a polymer emulsion is used as seed particles. The method being developed for introducing the vinyl monomer can be applied. For example, Jo
urinal of Dispersion Science
ce & Technology, 5: 231 (19
1984), a synthetic emulsion particle is used as a seed particle, and an active energy ray-curable compound is added thereto to simply absorb and enlarge the particle.
kromouleChemistry, 180
Vol., P. 737 (1979), a method of introducing an active energy ray-curable compound into emulsion particles, or a molecular diffusion method, a dynamic swelling method, a diffusion swelling method. There is a method of introducing an active energy ray-curable compound into emulsion particles using a technique called a method.

As a concrete example, there may be mentioned a method in which an active energy ray-curable compound is used as an aqueous dispersion and the aqueous dispersion is added to emulsion particles as seed particles and mixed by stirring.

In order to smoothly introduce the active energy ray-curable compound into the emulsion particles, the aqueous dispersion of the active energy ray-curable compound can be emulsified at a high concentration with a small amount of an emulsifier so that the dispersion stability is deteriorated to some extent. Is prepared. Examples of emulsifiers that can be used here include the above-mentioned various emulsifiers, and among the emulsifiers exemplified above, for example, sodium dodecylbenzenesulfonate is preferable.
The amount of the emulsifier used is about 5% by weight or less, preferably 0.05 to 5% by weight, based on the active energy ray-curable compound. The concentration of the aqueous dispersion added and mixed by stirring is about 5 to 50% by weight, preferably 20 to 40% by weight.

The method of adding the aqueous dispersion to the emulsion particles may be batch addition, continuous addition or intermittent addition, or a combination thereof. Further, the concentration of the emulsion particles when adding the aqueous dispersion is 10 to
It is about 50% by weight, preferably 15 to 35% by weight.
The temperature at the time of addition is about 20 to 70 ° C., preferably 3
0-50 ° C.

Further, when it is attempted to introduce 50% by weight or more of the active energy ray-curable compound with respect to the solid content of the emulsion particles into the emulsion particles, or the active energy ray-curable compound has low solubility in water. In some cases, when these compounds are introduced into the emulsion particles, the migration of these compounds into the emulsion particles may not proceed sufficiently, the dispersion stability may decrease, and aggregates of the emulsion mixture may occur. In such a case, in order to promote the migration of these compounds into the emulsion particles, for example, as in the case of the molecular diffusion method among seed polymerization, the aqueous dispersion of the compound to be added is homogenized. It is effective to use, for example, a method in which the particles are forcibly dispersed more finely than the emulsion particles to be seed particles and then added. Further, a method in which a small amount of a low water-soluble compound is introduced into the emulsion particles serving as seed particles in advance and then an aqueous dispersion of the active energy ray-curable compound is added and stirred can also be performed. As the low water-soluble compound, a solvent having a very low water solubility such as 1-chlorododecane can be exemplified, and the method of introducing the low water-soluble compound into the emulsion particles is the active energy ray-curable compound described above in the emulsion particles. A method similar to the method introduced in can be used. The amount of the low water-soluble compound introduced is 30% by weight or less, preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the solid content of the emulsion particles.

By the method described above, an active energy ray-curable emulsion containing an active energy ray-curable compound inside the emulsion particles can be obtained. Further, in order to impart various functions to the active energy ray-curable emulsion of the present invention, if necessary,
Thermal polymerization inhibitor, colorant, extender pigment, plasticizer, lubricant, stabilizer, flame retardant, defoaming agent, antioxidant, bactericide, conductive material,
Additives such as magnetic materials can be included.

[0028]

The active energy ray-curable emulsion of the present invention has good dispersion stability and film-forming property, and the cured product of the emulsion is excellent in water resistance, solvent resistance, weather resistance, mechanical properties and the like. Also, as emulsion particles that become seed particles,
In particular, three-dimensionally crosslinked ones are emulsions having a high crosslinking density and suitable for applications in which the water resistance and weather resistance of cured films such as paints, printing inks, surface coating materials and photoresists are required. Further, the active energy ray-curable emulsion of the present invention has a high degree of freedom in designing emulsion particles as seed particles, and it is possible to freely select and use an active energy ray-curable compound that is generally commercially available and used. Compared with the more known active energy ray-curable emulsion, the degree of freedom in product design is high and the manufacturing method is simple.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Incidentally,% is based on weight.

Production Example 1 In a 1 L reaction vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, 440 g of ion-exchanged water and an oligoester acrylate-based polymerizable emulsifier having two or more polymerizable functional groups ( Brand name New Frontier A-229E, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. 22 g and copper sulfate 0.24 mg
After adding and stirring, the pH was adjusted to 3.5 with a 28% aqueous ammonia solution. Furthermore, methyl methacrylate 2
Add 8.8 g, butyl acrylate 12.3 g and sodium thiosulfate 0.4 g, and add nitrogen gas at 30 ° C.
Stir at and mix. Polymerization was then initiated by adding 14 g of 5% aqueous ammonium persulfate solution. Methyl methacrylate 1 at the stage when the heat generated by the polymerization started
A mixed solution of 31 g and 56.1 g of butyl acrylate was added dropwise over 2 hours. At this time, the dropping rate was adjusted so that the temperature did not exceed 60 ° C. After the dropping was completed, the temperature was kept at 60 ° C. for 3 hours to obtain an emulsion having an average particle diameter of 81 nm.

Example 1 Ion-exchanged water was added to the emulsion obtained in Production Example 1 in an amount of 96.
After adjusting the concentration to 15% by weight by adding 3.8 g, 4
Cooled to 0 ° C. To this emulsion having a concentration of 15% by weight, 50 g of pentaerythritol tetraacrylate (trade name: Beamset 710, manufactured by Arakawa Chemical Industry Co., Ltd.),
Photopolymerization initiator Darocur 1173 (manufactured by Merck) 1.5
g, 0.1 g of sodium laurylbenzenesulfonate and 91.2 g of ion-exchanged water (JAN
Emulsified with KE & KUNKEL (10000 rpm,
The resulting dispersion was added for 5 minutes and stirred at room temperature for 5 hours to obtain an emulsion of the present invention having an average particle diameter of 86 nm in which the active energy ray-curable compound was introduced inside the emulsion particles.

Production Example 2 In a 1 L reaction vessel equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a reflux cooling tube, 440 g of ion-exchanged water and an oligoester acrylate-based polymerizable emulsifier having two or more polymerizable functional groups ( Brand name New Frontier A-229E, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. 22 g and copper sulfate 0.24 mg
After adding and stirring, the pH was adjusted to 3.5 with a 28% aqueous ammonia solution. Furthermore, methyl methacrylate 2
2.6 g, butyl acrylate 18.5 g and sodium thiosulfate 0.4 g were added, and nitrogen gas was passed through at 30 ° C.
Stir at and mix. Polymerization was then initiated by adding 14 g of 5% aqueous ammonium persulfate solution. Methyl methacrylate 1 at the stage when the heat generated by the polymerization started
A mixed solution of 02.9 g and butyl acrylate 84.2 g was added dropwise over 2 hours. At this time, the dropping rate was adjusted so that the temperature did not exceed 60 ° C. After the completion of dropping, the temperature was kept at 60 ° C. for 3 hours to obtain an emulsion having an average particle diameter of 83 nm.

Example 2 Ion-exchanged water was added to the emulsion obtained in Production Example 2 in an amount of 96.
After adjusting the concentration to 15% by weight by adding 3.8 g, 4
Cooled to 0 ° C. First, 12.5 g of 1-chlorododecane, 0.025 g of sodium laurylbenzenesulfonate, and 23.2 g of ion-exchanged water were added to this homogenizer (JANKE & K).
A dispersion liquid emulsified (10000 rpm, 5 minutes) with UNKEL) was added, and the mixture was stirred at 40 ° C. for 5 hours to obtain an emulsion in which 1-chlorododecane was introduced inside the emulsion particles. Successively, in the emulsion, 125 pentaerythritol tetraacrylate (trade name: Beamset 710, manufactured by Arakawa Chemical Industry Co., Ltd.)
g, photoinitiator Darocur 1173 (manufactured by Merck)
3.75 g, sodium laurylbenzenesulfonate 0.25 g and ion-exchanged water 228.4 g were emulsified by a homogenizer (manufactured by JANKE & KUNKEL) (10
(000 rpm, 5 minutes) was added, and the mixture was stirred at room temperature for 12 hours so that the inside of the emulsion particles became
Average particle size 9 with active energy ray-curable compound introduced
A 0 nm emulsion of the invention was obtained.

Production Example 3 In a 1 L reaction vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser tube, 440 g of ion-exchanged water, a non-polymerizable emulsifier of a phosphoric acid ester type (trade name PRYSURF A212)
E, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 22 g and copper sulfate 0.2
After adding 4 mg and stirring, the pH was adjusted to 3.5 with a 28% aqueous ammonia solution. Furthermore, 22.6 g of methyl methacrylate, 18.5 g of butyl acrylate, and 0.4 g of sodium thiosulfate were added, and while passing nitrogen gas,
Stir and mix at 0 ° C. Polymerization was then initiated by adding 14 g of 5% aqueous ammonium persulfate solution. When heat generation due to polymerization started, a mixed solution of 102.9 g of methyl methacrylate and 84.2 g of butyl acrylate was added dropwise over 2 hours. At this time, the dropping rate was adjusted so that the temperature did not exceed 60 ° C. After the dropping was completed, the temperature was kept at 60 ° C. for 3 hours to obtain an emulsion having an average particle size of 64 nm.

Example 3 Ion-exchanged water was added to the emulsion obtained in Production Example 3 in an amount of 96.
After adjusting the concentration to 15% by weight by adding 3.8 g, 4
Cooled to 0 ° C. First, 12.5 g of 1-chlorododecane, 0.025 g of sodium laurylbenzenesulfonate, and 23.2 g of ion-exchanged water were added to this homogenizer (JANKE & K).
A dispersion liquid emulsified (10000 rpm, 5 minutes) with UNKEL) was added, and the mixture was stirred at 40 ° C. for 5 hours to obtain an emulsion in which 1-chlorododecane was introduced inside the emulsion particles. Successively, in the emulsion, 125 pentaerythritol tetraacrylate (trade name: Beamset 710, manufactured by Arakawa Chemical Industry Co., Ltd.)
g, photoinitiator Darocur 1173 (manufactured by Merck)
3.75 g, sodium laurylbenzenesulfonate 0.25 g and ion-exchanged water 228.4 g were emulsified by a homogenizer (manufactured by JANKE & KUNKEL) (10
(000 rpm, 5 minutes) was added, and the mixture was stirred at room temperature for 12 hours so that the inside of the emulsion particles became
Average particle size 8 with active energy ray-curable compound introduced
A 1 nm emulsion of the invention was obtained.

Experimental Example 4 In a flask equipped with a stirrer, a commercially available crosslinked acrylic emulsion (trade name: Microgel E2002, manufactured by Nippon Paint Co., Ltd., solid content 35%, average particle size 73 nm) 1
00 g and 133.3 g of ion-exchanged water were added and mixed with stirring to adjust the concentration of the emulsion to 15%. The temperature of this emulsion is raised to 40 ° C., and while stirring, first,
1.8 g of 1-chlorododecane, 0.004 g of sodium laurylbenzenesulfonate and 3.4 of deionized water
g homogenizer (manufactured by JANKE & KUNKEL)
The dispersion liquid emulsified in (10000 rpm, 5 minutes) was added, and the mixture was stirred at 40 ° C. for 2 hours to obtain an emulsion in which 1-chlorododecane was introduced inside the emulsion particles. Next, add pentaerythritol tetraacrylate (trade name: Beamset 7) to the emulsion.
10, Arakawa Chemical Industry Co., Ltd. 17.5 g, photopolymerization initiator Darocur 1173 (Merck) 0.53 g, sodium laurylbenzene sulfonate 0.04 g and ion-exchanged water 32 g homogenizer (JANKE & KU).
The present invention having an average particle diameter of 77 nm in which an active energy ray-curable compound is introduced into emulsion particles by adding a dispersion liquid (10000 rpm, 5 minutes) emulsified with NKEL) and stirring at room temperature for 12 hours. An emulsion of

Comparative Example 1 Bisphenol A ethylene oxide modified acrylate (trade name: Beamset 750, manufactured by Arakawa Chemical Industry Co., Ltd.)
50 g, a photopolymerization initiator Darocur 1173 (manufactured by Merck) 1.5 g, an emulsifier (trade name: Emulgen 920, manufactured by Kao Co., Ltd.) 5 g, and ion-exchanged water 91.2 g are mixed by stirring at room temperature. An active energy ray-curable compound emulsion was obtained.

Comparative Example 2 The emulsion obtained in Production Example 1 was mixed with ion-exchanged water 96 times.
After adding 3.8 g to adjust the concentration to 15% by weight, the mixture was cooled to room temperature. Pentaerythritol tetraacrylate (trade name: Beamset 71
0, Arakawa Chemical Co., Ltd. 50 g, photopolymerization initiator Darocur 1173 (Merck) 1.5 g, emulsifier (trade name Emulgen 920, Kao Co., Ltd.) 5 g, and ion-exchanged water 91.2 g. The dispersion was added and stirred to obtain an emulsion mixture composed of crosslinked polymer emulsion particles and an emulsion of an active energy ray-curable compound.

Dispersion stability (storage stability), film-forming property and curability of the emulsions obtained in Examples and Comparative Examples, and water resistance, solvent resistance and mechanical properties (hardness) of cured products of the emulsions. Was evaluated. Table 1 shows the evaluation results. In addition,
The particle diameters of the emulsions obtained in Production Examples and Examples were measured with a laser particle meter measuring device manufactured by Otsuka Electronics Co., Ltd.

(Dispersion stability (storage stability)) The obtained emulsion was stored at 25 ° C., and the state after 1 week was visually observed according to the following criteria. ◯: Separation and sedimentation do not occur. Δ: Some separation and sedimentation is observed. X: There is a large amount of precipitate.

(Film forming property) The obtained emulsion was coated on a glass plate with a bar coater so that the dry coating amount was 20 g / m ^2, and the state of the dried film after drying at 45 ° C. for 1 hour was as follows. Was evaluated according to the standard. ◯: No cracks occurred. Δ: Partial cracking occurred. X: Cracks were generated on the whole.

(Curability) The obtained emulsion was coated on a glass plate with a bar coater so that the dry coating amount was 20 g / m ² , and dried at 45 ° C. for 1 hour. The dried film on the glass plate was passed through an ultraviolet irradiation device having an 80 W / cm high-pressure mercury lamp (3 seconds irradiation), the surface of the cured film was touched with a finger, and the degree of stickiness was evaluated according to the following criteria. ◯: Hardened (no stickiness on the surface). X: Not cured (there is stickiness on the surface).

(Water resistance) Ion-exchanged water 5 on the surface of the cured film
The mL was dropped and the lid was covered with a petri dish. After 24 hours, the ion-exchanged water was wiped off, and the state of the surface of the cured film was visually observed according to the following criteria. ：: No change. Δ: Swelling slightly. X: Whitening.

(Solvent resistance) Ethanol 5 on the surface of the cured film
The mL was dropped and the lid was covered with a petri dish. After 24 hours, ethanol was wiped off, and the state of the surface of the cured film was visually observed according to the following criteria. ：: No change. Δ: Swelling slightly. X: Dissolved

(Mechanical properties (pencil hardness)) JIS K
According to 5400 pencil scratch test.

[0046]

[Table 1]

Claims (10)

[Claims] 1. An active energy ray curable emulsion comprising an active energy ray curable compound inside emulsion particles. 2. An active energy ray curable emulsion comprising an ultraviolet curable compound and a photopolymerization initiator inside emulsion particles. 3. The active energy ray-curable emulsion according to claim 1, wherein the emulsion particles are three-dimensionally crosslinked. 4. The active energy ray-curable emulsion according to claim 1, wherein the emulsion particles are a polymer emulsion obtained by reacting a vinyl monomer and an emulsifier. 5. The active energy ray-curable emulsion according to claim 4, wherein the vinyl monomer contains a crosslinkable vinyl monomer. 6. The active energy ray-curable emulsion according to claim 4, wherein the emulsifier contains a polymerizable emulsifier. 7. The active energy ray-curable emulsion according to claim 6, wherein the polymerizable emulsifier has at least two polymerizable functional groups in the molecule. 8. An active energy ray-curable compound is emulsified into an aqueous dispersion, and the aqueous dispersion is mixed with emulsion particles so that the active energy ray-curable compound is contained inside the emulsion particles. Claim 1
A method for producing the active energy ray-curable emulsion described. 9. An emulsion particle in which an ultraviolet curable compound and a photopolymerization initiator are emulsified to prepare an aqueous dispersion, and the ultraviolet dispersion compound and the photopolymerization initiator are contained inside the emulsion particle. The method for producing an active energy ray-curable emulsion according to claim 2, wherein the emulsion is mixed with. 10. The method for producing an active energy ray-curable emulsion according to claim 8, wherein the low water-soluble compound is introduced into the emulsion particles in advance before the aqueous dispersion is mixed with the inside of the emulsion particles. .