KR100508967B1 - Method for Preparing a Microcapsule with Uniform Size and Morphology - Google Patents

Abstract

The present invention relates to a method for producing a microcapsule having a uniform size and shape, and a monomer, a crosslinking agent, a hydrophilic comonomer, an emulsifier, a hydrophobic agent, a hydrophobic substance, an initiator, and deionized water are put into a reactor to form a mini emulsion. ; And a polymerization step of polymerizing the mini-emulsion using an oil-soluble initiator in the application of an initiator to form a polymer. The microcapsules of uniform size and shape by inhibiting the formation of secondary particles by using an oil-soluble initiator. There is an effect that can provide.

Description

Method for Preparing a Microcapsule with Uniform Size and Morphology

The present invention relates to a method for producing a microcapsule having a uniform size and shape. More specifically, the monomer particles are stabilized by the osmotic pressure of the hydrophobic agent, so that the hydrophobic material dissolved in the monomer particles is uniformly positioned inside the microcapsule, and the oil-soluble initiator is used to suppress the formation of the secondary particles so that the uniform size and It relates to a method for producing a microcapsule capable of producing a microcapsule in the form.

Microcapsules are particles ranging from tens of nanometers to hundreds of microns, with nuclear material in the form of molecules of liquid or solid inside, surrounded by a wall of polymeric material. The nuclear material may include pharmaceuticals, perfumes, catalysts, dyes, and the like, and microcapsules are currently used in various industrial fields.

Conventional microcapsules manufacturing method is to obtain a post-treatment of the polymer. (Chem. Soc. Rev., 2000, 29, 295) It mixes insoluble polymer, organic solvent and material to be put in inner core, then stirs enough to make it uniform and removes organic solvent. That's how.

For example, US Pat. No. 4,384,975 describes the inhibition of solvents by vacuum distillation. This method has a problem that does not contain a variety of organic materials. In addition, in British Patent No. 1,394,780, a solvent is removed by evaporation, and this method has a problem in that it takes a long time to prepare a microcapsule.

In addition, US Pat. No. 3,891,570 discloses a method of extracting the removal of the organic solvent with water by heating the aqueous dispersion or vacuum by the method of removing the polymer solvent. However, since this method is a method of preparing microcapsules through removal of organic solvents, it is impossible to encapsulate a material that volatilizes at a low temperature, that is, a small molecular weight (less than 500 Daltons), and thus is applicable only in a specific system. .

Another manufacturing method is to make the material forming the outer wall through interfacial polymerization. Korean Patent No. 0,272,616 suggests a manufacturing method having an outer wall of polyurea. This method is limited because the type of the polymer that forms the outer wall must be made by interfacial polymerization, and the particle size distribution of the final microcapsules is wide, and the size of the particles is very large (1 μm or more), and the volume of the reaction system is large. There was a problem that a large amount obtained was small.

In addition, US Pat. No. 5,545,504 discloses a miniemulsion polymerization method including 1 to 30 parts by weight of heterogeneous polymers therein. Heterogeneous polymer materials have been proposed to produce a hybrid material having a uniform size by using a toner material used in ink as a support, but there is a problem that only the polymer can be included in the final manufacturing material.

In Langmuir, 2001, 17 and 908, microcapsules were prepared using PMMA and hexadecane. PMMA has polarity, but because hexadecane is a nonpolar material, hexadecane is completely enclosed in PMMA and placed inside, and PMMA forms a dispersion in water. At this time, the nuclear material in the microcapsules was limited to a material having a very low solubility in water, such as hexadecane, which has a problem in that its use is limited.

In order to solve the above problems, an object of the present invention is to provide a manufacturing method for producing a microcapsule of uniform size and shape by inhibiting the formation of secondary particles using an oil-soluble initiator.

In addition, an object of the present invention is to provide a microcapsules produced by the above production method.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention to achieve the above object.

A method for preparing a microcapsule, the method comprising: forming a monomer, a crosslinking agent, a hydrophilic comonomer, an emulsifier, a hydrophobic agent, a hydrophobic substance, an initiator, and deionized water into a reactor to form a mini emulsion; And a polymerization step of polymerizing the mini-emulsion using an oil-soluble initiator in the application of the initiator to form a polymer.

The composition ratio of the reactive component in the mini-emulsion forming step is 0.01 to 1.0 parts by weight of emulsifier, 0.5 to 10 parts by weight of hydrophobic material, 10 to 70 parts by weight of hydrophobic material, 0.1 to 10 parts by weight of crosslinking agent, hydrophilic comonomer 0.1 to 10 parts by weight and 0.1 to 3 parts by weight of initiator.

The temperature of the polymerization reaction in the mini-emulsion polymerization step may be 25 to 160 ℃, the time of the polymerization reaction may be 3 to 24 hours.

The monomer is a compound having an unsaturated double bond in which polymerization proceeds as a free radical, methacrylate derivative, acrylate derivative, acrylic acid derivative, methacrylonitrile, ethylene, butadiene, isoprene, styrene and styrene derivative, acrylonitrile At least one may be selected from the group consisting of derivatives, vinyl ester derivatives, vinyl halide derivatives and mercaptan derivatives.

The hydrophobic agent is dissolved in water at 25 ° C. at 5 × 10 ⁻⁶ g / kg or less, C ₁₂ to C ₂₀ aliphatic alcohols, C ₁₂ to C ₂₀ alkyl group having carbon number up to C ₂₀ , C _At least one selected from the group consisting of alone or mixtures of alkyl mercaptans from ₁₂ to C ₂₀ , organic dyes, fluorinated alkanes, silicone oil compounds, natural and synthetic oils, oligomers and polymers with molecular weights from 1000 to 500,000. .

The emulsifier may be at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers.

The crosslinking agent is a monomer having two or more unsaturated bonds copolymerizable with the main reaction monomer, allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimethacrylate, Neopentyl glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate and divinylbenzene It may be selected from one or more of the group consisting of.

The hydrophilic comonomers can be unsaturated carboxylic acids and / or unsaturated polycarboxylic acid alkyl esters.

The unsaturated carboxylic acid may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid.

The unsaturated polycarboxylic acid alkyl ester may be at least one selected from the group consisting of itaconic acid monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester.

The hydrophobic materials include C ₄ to C ₂₀ hydrocarbons and isomers thereof, C ₁₀ to C ₂₀ aliphatic and aromatic alcohols, C ₁₀ to C ₂₀ aliphatic and aromatic esters and C ₁₀ to C ₂₀ aliphatic and aromatic At least one may be selected from the group consisting of ethers.

The initiator may be at least one selected from the group consisting of oil-soluble initiators having a solubility in water of 0.5 g / kg or less at 25 ° C. in the group consisting of peroxides, peroxide initiators, azo initiators and redox initiators.

The present invention also provides a microcapsules produced by the above method.

The microcapsule has a size of 100 to 2500nm, has a liquid or solid nuclear material in the outer wall, the volume of the nuclear material may be 10 to 80% of the total volume.

Hereinafter, the present invention will be described in detail.

The present invention is based on 100 parts by weight of monomer

a) 0.01 to 1.0 parts by weight of an emulsifier selected from the group consisting of a nonionic emulsifier, a cationic emulsifier, an anionic emulsifier, and an amphoteric emulsifier;

b) aliphatic hydrocarbons, C ₁₂ -C ₂₀ acids, C ₁₂ -C ₂₀ aliphatic alcohols, C ₁₂ acrylate, up to C ₁₂ -C ₂₀ consisting of an alkyl group having a carbon number of -C ₂₀ alkyl mercaptans 5 × 10 ⁻⁶ g / kg or less at 25 ° C. in water alone or in a mixture of these, organic dyes, fluorinated alkanes, silicone oil compounds, natural and synthetic oils, and oligomers and polymers having molecular weights from 1000 to 500,000. 0.5 to 10 parts by weight of an ultrahydrophobe, one or two or more selected from soluble materials;

c) Hydrocarbons up to C ₄ -C ₂₀ which are compatible with monomers to form nuclear materials, have greater interfacial tension with water than the interfacial tension between the polymer forming the outer wall and the water, and are incompatible with the polymer. and its isomers, 1 from the aliphatic and aromatic ethers, or all of the compounds belonging to the Jiangsu hand of aliphatic and aromatic esters to, C ₁₀ -C _20, of aliphatic and aromatic alcohols to, C ₁₀ -C ₂₀ in C ₁₀ -C ₂₀ 10 to 70 parts by weight of species or two or more selected hydrophobic materials:

d) 0.1 to 10 parts by weight of a crosslinking agent having two or more unsaturated bonds;

e) It is a substance that introduces hydrophilicity into the polymer to help the polymer make up the outer wall of the particles.It is unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, monoethyl ester, 0.1 to 10 parts by weight of a hydrophilic comonomer selected from the group consisting of monomers composed of unsaturated polycarboxylic acid alkyl esters having at least one carboxyl group such as fumaric acid monobutyl ester and maleic monobutyl ester;

f) Minii, including 0.1 to 3 parts by weight of one or more initiators selected from oil-soluble initiators having a solubility in water of 0.5 g / kg or less at 25 ° C in the group consisting of peroxide initiators, azo initiators, and redox initiators. Forming a mullion (forming step); And polymerizing or reacting the miniemulsion in a stable state for a time sufficient to form a polymer (polymerization reaction step).

The oil-soluble initiator in the present invention prevents the formation of secondary particles, such that microcapsules having a uniform size and shape are produced. Here, the secondary particles are not latex particles formed through polymerization of monomer particles including hydrophobic materials formed through homogenization, but particles containing no hydrophobic materials formed by polymerization and magnetic particle polymerization of monomers in an aqueous phase. Say.

By the application of oil-soluble initiators, the initiator is located only in the monomer particles, not in the water phase, which serves to suppress secondary particle formation by inhibiting the possibility that a small amount of monomer dissolved in the water phase meets with the initiator to cause polymerization. In addition, it is known that particles of 50 to 500 nm size may be produced when preparing particles through general miniemulsion polymerization, but the present invention has introduced a method of preparing stable particles having a size of 2500 nm.

In the present invention, a monomer having a double bond and capable of free radical polymerization has a monomer having an interfacial tension between water and a monomer smaller than that between a nuclear material and water, that is, styrene, α-methyl styrene, and p-nitro styrene. , Ethylvinylbenzene, vinylnaphthalene, methyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n- Hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, ste Aryl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohex Sil methacrylate, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, phenylpropyl acrylate, phenylpropyl methacrylate, phenylnonyl acrylate, phenylnonyl methacrylate, 3-methicone Methoxybutyl acrylate, 3-methoxybutyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, tri Ethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, furfuryl acrylate, furfuryl methacrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, acrylo Nitrile, vinyl acetate , Vinyl pivalate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate, and the like. It doesn't happen.

The emulsifiers include sulfonates, carboxylates, rosinates, sulfosuccinates and metal salts thereof, such as alkylbenzene sulfonic acids, sodium alkylbenzene sulfonates, alkyl sulfonic acids, sodium alkyl sulfonates and sodium poly Anionic emulsifiers which are widely used in general emulsion polymerization of oxyethylene nonylphenyl ether sulfonate, sodium stearate, sodium dodecyl sulfate, sodium dodecyl lycinate, abietin acid and the like; Cationic emulsifiers such as higher amine halides, quaternary ammonium salts and alkylpyridinium salts; One or more types can be selected from the group which consists of nonionic emulsifiers, such as polyvinyl alcohol and polyoxyethylene nonylphenyl, It is not limited to these emulsifiers.

As the hydrophobic agent (强 疏 水劑, ultrahydrophobe) is a substance that is dissolved in water less than 5.0 x 10 ^-6 g / kg is suitable. The most suitable hydrophobic agent is an alkane having 12 or more carbon atoms and a substance including isomers such as alcohol, hexadecane, heptadecane, octadecane, cetyl alcohol, isopropyl laurate, isopropyl palmitate, hexyl laurate, isopropyl myristate , Myristyl myristate, cetyl myristate, 2-octyldecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate and 2-octyldodecyloleate, glycol ester oils, eg For example, polypropylene glycol monooleate and neopentyl glycol 2-ethylhexanoate and polyalcohol ester oils, isostearate, triglycerides and coco fatty acid triglycerides, almond oil, apricot oil, avocado oil, theobroma Oil, carrot seed oil, castor oil, citrus seed oil, coconut oil, Sorghum oil, cottonseed oil, cucumber oil, egg oil, jojoba oil, lanolin oil, linseed oil, mineral oil, mink oil, olive oil, palm oil, phosphorus oil, peach phosphorus oil, peanut oil, rape seed oil, safflower oil, sesame oil, shark liver oil, Alkyl mercaptans such as soybean oil, sunflower seed oil, sweet almond oil, tallow, sheep oil, turtle oil, vegetable oil, whale oil and wheat germ oil, organosilicon, siloxane, n-dodecyl mercaptan, t-dodecyl mercaptan For example, the fluoride alkanes such as hexafluorobenzene may be used alone or in combination of two or more thereof, but is not limited thereto.

As the initiator, an initiator having a solubility in water of 0.5 g / kg or less at 25 ° C. is suitable, and an initiator having a solubility of 0.02 g / kg or less is preferable. One or more types can be used from the group which consists of a peroxide type initiator, an azo type initiator, and a redox type initiator, It is not limited to these.

The crosslinking agent is used to provide the function of controlling the strength of the outer wall and the diffusion of the inner material, for example allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimetha Acrylate, neopentyl glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate and Divinylbenzene and the like are known, but are not limited thereto and refer to a monomer having two or more unsaturated bonds copolymerizable with the main reaction monomer.

The hydrophilic comonomer is a compound capable of increasing the hydrophilicity of the polymer produced through copolymerization with the main reaction monomer to help the hydrophobic material to be stably located in the outer wall of the polymer and having compatibility with the main reaction monomers, and is copolymerizable. For example, unsaturated polycarboxylic acids having at least one carboxyl group such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid and itaconic acid monoethyl ester, fumaric acid monobutyl ester, and maleic acid monobutyl ester One or more types may be selected from the monomer group consisting of carboxylic acid alkyl esters, but is not limited thereto.

Hydrophobic materials are compatible with monomers, but have higher interfacial tension to water than polymers that make up the outer wall. There should be no surname.

These materials will vary depending on the polymers that make up the outer wall, but generally include aliphatic and aromatic hydrocarbons, hexane, heptane, cyclohexane, octane, nonane, decane, benzene, toluene xylene, and C ₄ -C ₂₀ hydrocarbons and isomers thereof. covers and encompasses aliphatic and aromatic ethers, silicone compounds, natural and synthetic oils of the aliphatic and aromatic esters to, C ₁₀ -C _20, of aliphatic and aromatic alcohols to, C ₁₀ -C ₂₀ in C ₁₀ -C _20.

And this hydrophobic material may be a material such as hydrophobic material. The hydrophobic material may be selected by mixing one or two or more of them, but is not limited thereto.

In addition, the hydrophobic material is not limited to a specific material having a lower solubility in water than a polymer, and includes all hydrophobic materials (most organic materials) compatible with monomers.

Putting the above-described material into the reactor, the method for preparing the particles may be a method of mechanical agitation such as Turrax, a method of using a homogenizer such as an ultrasonic generator, a microfluidizer, Gaulin Homogenizer.

Generally, the polymerization reaction temperature is 25 to 160 ° C, preferably 40 to 90 ° C, and the polymerization reaction time is 3 to 24 hours, preferably 4 to 10 hours.

Through the manufacturing method as described above it can be produced a microcapsule of a certain size including a hydrophobic material. At this time, the microcapsule of the present invention is composed of a) the outer wall of the polymer, b) the inner nucleus made of a hydrophobic material, the hydrophobic material occupies 10 to 80%, preferably 30 to 60% of the total volume do.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

[Examples 1-3]

After mixing the components according to the composition shown in Table 1, using a homogenizer to make a mini-emulsion particles, and reacted by heating at 90 ℃ in a nitrogen-substituted polymerization reactor in a batch form, and reacted for 10 hours The reaction was terminated. The obtained polymer particles were analyzed, and the results are shown in Table 1 below.

[Comparative Examples 1 and 2]

It was carried out under the same reactive ingredients and conditions as in Example 1 by applying the potassium phosphate persulfate as a water-soluble initiator to prepare the polymer particles in the composition ratio of the reaction components shown in Table 1 below and the results are shown in Table 1 below.

Reactive cohesion and centrifugation results Raw material name Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Styrene 100 100 100 100 100 Butanediol dimethacrylate (crosslinking agent) 8 8 4 8 8 Methacrylic acid 8 8 4 8 4 Hexadecane 3.6 3.6 3.6 3.6 3.6 Isooctane 50 50 50 50 50 Benzoyl peroxide 0.5 0.5 0.5 × × Potassium Persulfate × × × 0.5 0.5 Sodium Lauryl Sulfate × 0.3 × × 0.3 Aerosol OT 0.3 × 0.3 0.3 × Deionized water 200 200 200 200 200 Centrifugal upper part (%) 98.32 98.71 97.91 68.01 72.03

Comparing the examples with the comparative examples, there was a difference in the particle size uniformity and particle shape of the microencapsulation applied to the example using the soluble benzoyl peroxide as the oil-soluble initiator and the potassium persulfate as the water-soluble initiator.

That is, in the case of the embodiment using the water-soluble initiator, the formation of the secondary particles having a small size without the hydrophobic material is clearly seen, whereas in the case of the embodiment using the oil-soluble initiator, a stable form of microcapsules having a uniform size was prepared.

Electron microscope

The latex obtained was analyzed using TEM. The results are shown in FIGS. Here, latex refers to the polymer particles are present in a state dispersed in water and the like.

As shown in Figures 1 and 2 it was confirmed that the polymer prepared in accordance with the present invention has a particle having a uniform size.

Centrifugation

The obtained latex was centrifuged at 15000 rpm for 1 hour to separate the upper and lower layers, and the ratio of the upper layers was shown in Table 1 above.

When the latex is centrifuged, the particles containing hydrophobic material are less dense than water, so they float upward to form upper layers. Secondary particles without hydrophobic material are denser than water and sink to precipitation. As can be seen whether the secondary particles are formed, the results of Table 1 showed that the example to which the oil-soluble initiator was applied showed a high upper portion ratio, and the formation of secondary particles was suppressed.

As described above, in the method for preparing a microcapsules according to the present invention, the monomer particles are stabilized by the osmotic pressure of the hydrophobic agent, so that the hydrophobic material dissolved in the monomer particles can be uniformly positioned inside the polymer, and the secondary particles are formed using the oil-soluble initiator. It is a useful invention that can suppress the formation of microcapsules having a uniform size and shape.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

1 and 2 show electron micrographs (TEM) of the polymer prepared according to the embodiment of the present invention.

Figure 3 shows an electron micrograph (TEM) of the polymer prepared according to the comparative example of the present invention.

Claims (14)

In the manufacturing method of the microcapsules, Forming a monomer, a crosslinking agent, a hydrophilic comonomer, an emulsifier, a hydrophobic agent, a hydrophobic substance, an initiator, and deionized water into a reactor to form a mini emulsion; And Polymerizing the miniemulsion using an oil-soluble initiator in the application of the initiator to form a polymer; Method of producing a microcapsule comprising a. The method of claim 1, In the mini-emulsion forming step, the composition ratio of the reactive component is 0.01 to 1.0 parts by weight of emulsifier, 0.5 to 10 parts by weight of hydrophobic material, 10 to 70 parts by weight of hydrophobic material, 0.1 to 10 parts by weight of crosslinking agent, and hydrophilic comonomer 0.1 to 10 parts by weight and 0.1 to 3 parts by weight of initiator is a method for producing a microcapsule. The method of claim 1, The method of producing a microcapsule, characterized in that the temperature of the polymerization reaction in the mini-emulsion polymerization step is 25 to 160 ℃, the polymerization reaction time is 3 to 24 hours. The method of claim 1, The monomer is a compound having an unsaturated double bond in which the polymerization proceeds as a free radical. A method for producing a microcapsule, characterized in that at least one selected from the group consisting of derivatives, vinyl ester derivatives, vinyl halide derivatives and mercaptan derivatives. The method of claim 1, The hydrophobic agent is dissolved in water at 25 ° C. at 5 × 10 ⁻⁶ g / kg or less, C ₁₂ to C ₂₀ aliphatic alcohols, C ₁₂ to C ₂₀ acrylates composed of alkyl groups having carbon number, C _At least one selected from the group consisting of a mixture or a mixture of alkyl mercaptans from ₁₂ to C ₂₀ , organic dyes, fluorinated alkanes, silicone oil compounds, natural and synthetic oils, oligomers and polymers having a molecular weight of 1000 to 500,000. Method for producing a microcapsule. The method of claim 1, The method of claim 1, wherein the emulsifier is selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers. The method of claim 1, The crosslinking agent is a monomer having two or more unsaturated bonds copolymerizable with the main reaction monomer, allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimethacrylate, Neopentyl glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate and divinylbenzene Method for producing a microcapsule, characterized in that at least one selected from the group consisting of. The method of claim 1, Wherein said hydrophilic comonomer is an unsaturated carboxylic acid and / or an unsaturated polycarboxylic acid alkyl ester. The method of claim 8, The unsaturated carboxylic acid is a method for producing a microcapsule, characterized in that at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid. The method of claim 8, And said unsaturated polycarboxylic acid alkyl ester is at least one selected from the group consisting of itaconic acid monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester. The method of claim 1, The hydrophobic materials include C ₄ to C ₂₀ hydrocarbons and isomers thereof, C ₁₀ to C ₂₀ aliphatic and aromatic alcohols, C ₁₀ to C ₂₀ aliphatic and aromatic esters and C ₁₀ to C ₂₀ aliphatic and aromatic Method for producing a microcapsule, characterized in that at least one selected from the group consisting of ether. The method of claim 1, Wherein the initiator is at least one selected from the group consisting of oil-soluble initiators having a solubility in water of not more than 0.5 g / kg at 25 ° C. in the group consisting of peroxides, peroxide initiators, azo initiators and redox initiators. Method of Making Capsules. Microcapsules made by the method of any one of claims 1 to 12. The method of claim 13, The microcapsule has a size of 100 to 2500nm, has a liquid or solid nuclear material in the outer wall, the volume of the nuclear material is 10 to 80% of the total volume of the microcapsule.