KR102145536B1 - Method for prreparing organic-inorganic hybrid microcapsule - Google Patents

Abstract

In the present invention, after preparing a continuous phase including an outer wall reinforcing material and inorganic particles of a capsule, a pickering emulsion is formed by mixing a reactive material or a dispersed phase including a reactive material and an active ingredient by using this, and the outer wall reinforcing material and the reactive material are interfacially formed. By allowing the polymerization to proceed in the biodegradable organic-inorganic hybrid microcapsule, which can stably support the active ingredient and then effectively express its activity by pressure, as well as exhibit the characteristic of being slowly released at room temperature unlike the conventional one It's about how.

Description

Manufacturing method of organic-inorganic hybrid microcapsules {METHOD FOR PRREPARING ORGANIC-INORGANIC HYBRID MICROCAPSULE}

The present invention relates to a method of manufacturing an organic-inorganic hybrid microcapsule, and more particularly, it is possible to effectively express the activity by pressure after stably supporting an active ingredient, and unlike the conventional method, it has a characteristic that is slowly released at room temperature. It relates to a method of manufacturing a biodegradable organic-inorganic hybrid microcapsule that can be represented.

Encapsulation is known as a method for solving the problem that the active ingredient loses its intrinsic properties due to factors such as light or heat during the storage period, or its concentration is low due to physical phenomena such as evaporation. Such encapsulation has the advantage of not only increasing the stability of the active ingredient, but also enabling the active ingredient to be activated at a time desired by the user, and thus is used in many industrial fields. A typical method of activating the encapsulated active ingredient is a method of gradually releasing or sustaining the active ingredient by inducing the destruction of the outer wall of the capsule due to factors such as pressure or the formation of a small hole in the outer wall of the capsule.

Melamine-formaldehyde resin-based capsules are known as an encapsulation material that is widely used commercially, but there is a problem that formaldehyde, which is a toxic substance, must exist in the manufacturing process of microcapsules. For this reason, interest in new capsules without formaldehyde is increasing.

As a solution to this, liposome capsules, coacervation, and microsponges have been proposed. However, these measures are insufficient to replace melamine capsules as they show limitations in that the stability of the capsule is reduced, the carrying capacity of the active ingredient is reduced, or the release is not controlled by the surfactant and ionic components in the formulation.

As another method, an inorganic material-based capsule such as silica has been proposed as a new alternative, but in the case of the capsule manufactured by the above method, as the amphiphilicity of the central material increases, it is difficult to form the outer wall after the precursor organopolysiloxane moves to the interface. There is a problem to apply it widely. In addition, the capsule has a disadvantage in that it is difficult to control the degree of activation of the active ingredient due to its low elasticity and high hardness.

On the other hand, there are capsules based on organic polymers that are widely used industrially, such as polyacrylic, polyurea, and polyurethane, and the capsules are considered as an alternative due to the advantages of not using formaldehyde in the polymerization process, wide versatility, and excellent economics. . However, due to the high elasticity of the polymer itself, the organic polymer-based capsule has difficulty in expressing the activity of the active ingredient because of the high elasticity of the polymer itself.

Therefore, there is a need to develop a biodegradable capsule material that has low toxic substances and has high versatility, has good economic efficiency, and can easily control the activity of active ingredients.

It is an object of the present invention to provide a biodegradable organic-inorganic hybrid microcapsule that has low toxic substances and has high versatility, has excellent economical efficiency, can easily express the activity of an active ingredient, and is slowly released at room temperature. It is to provide a manufacturing method.

Another object of the present invention is to provide a microcapsule comprising a biodegradable organic-inorganic hybrid outer wall manufactured by the above method.

A first step of preparing a second continuous solution containing a first continuous solution containing inorganic particles of the present invention and a polymer precursor 1 for reinforcing the outer wall;

A second step of preparing a biodegradable polymer precursor 2 reacting with the polymer precursor 1 for reinforcing the outer wall, or a dispersion phase solution including an active ingredient and the polymer precursor 2; And

A third step of forming a pickering emulsion by adding a dispersion phase solution to the first solution, and then forming the outer wall of the capsule by interfacial polymerization by adding a second solution, and

The outer wall of the capsule contains poly(β-amino ester) and inorganic particles,

The outer wall reinforcing polymer precursor 1 and the biodegradable polymer precursor 2 each independently contain one or more precursors for forming poly(β-amino ester),

It provides a method of manufacturing a biodegradable organic-inorganic hybrid microcapsule.

According to another embodiment of the present invention, a capsule according to the above method, comprising a dispersion phase positioned in a core and a hybrid capsule outer wall surrounding the outside of the dispersion phase, and comprising a dispersion phase of 1 to 90% by weight based on the total weight of the capsule It provides a biodegradable organic-inorganic hybrid microcapsule.

In the present invention, there are few toxic substances and not only have high versatility, but also have good economy, and the activity of the active ingredient can be easily expressed by controlling the strength of the outer wall of the capsule, and the internal dispersed phase is slowly released over time. There is an effect of providing a biodegradable organic-inorganic hybrid capsule.

In addition, the present invention has the effect of providing an eco-friendly organic-inorganic hybrid capsule when using a natural polymer, a derivative thereof, and a natural-derived polymer as a precursor during capsule manufacturing.

1 schematically shows the contact angle of inorganic particles.
Figure 2 shows the principle of the manufacturing method of the biodegradable organic-inorganic hybrid capsule of the present invention
3 shows a comparison of the release behavior of volatile oils over time in Comparative Examples 1 and 2 and Examples 1 and 6 to 8.
4 is a view showing a comparison of the washing evaluation results of Comparative Examples 3 to 4 and Example 10.

The present invention will be described in detail below and exemplify specific embodiments, which can be variously changed and have various forms. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, the meaning of "comprising" as used in the specification of the present invention specifies a specific characteristic, region, integer, step, operation, element and/or component, and other characteristics, region, integer, step, operation, element and/or It does not exclude the presence or addition of ingredients.

Further, in general, the diameter of the microcapsules may range from 1 to 1,000 μm. In the context of the present invention, the term “microcapsule” also includes nanocapsules, ie capsules with a diameter of <1 μm. However, the diameter of the capsule is preferably in the range of 1 to 100 μm, preferably 2 to 50 μm. The wall thickness can be, for example, 0.05 to 10 μm.

Hereinafter, a method of manufacturing a biodegradable organic-inorganic hybrid microcapsule according to a specific embodiment of the present invention, and a microcapsule manufactured using the same will be described.

In order to solve the conventional problem, the present invention includes a first step of including an outer wall reinforcing material capable of forming inorganic particles and a specific biodegradable polymer poly(β-amino ester) in a continuous phase, the outer wall reinforcing material and A second step of including a specific acrylate-based reactive material or active ingredient capable of reacting to form poly(β-amino ester) and the reactive material, and mixing the continuous phase and the dispersed phase to form a pickering emulsion, and then forming the outer wall of the capsule. It is intended to provide a biodegradable organic-inorganic hybrid microcapsule material including a third step of polymerization.

Preferably, the outer wall of the capsule may include an organic-inorganic hybrid structure including poly(β-amino ester) and inorganic particles.

Specifically, according to an embodiment of the present invention, a first step of preparing a continuous second solution containing a first continuous solution containing inorganic particles and a polymer precursor 1 for strengthening the outer wall;

A second step of preparing a biodegradable polymer precursor 2 reacting with the polymer precursor 1 for reinforcing the outer wall, or a dispersion phase solution including an active ingredient and the polymer precursor 2; And

A third step of forming a pickering emulsion by adding a dispersion phase solution to the first solution, and then forming the outer wall of the capsule by interfacial polymerization by adding a second solution, and

The outer wall of the capsule contains poly(β-amino ester) and inorganic particles,

The outer wall reinforcing polymer precursor 1 and the biodegradable polymer precursor 2 each independently contain one or more precursors for forming poly(β-amino ester),

A method of manufacturing a biodegradable organic-inorganic hybrid microcapsule is provided.

In the present invention, a continuous phase including an outer wall reinforcing material and inorganic particles is prepared so as to contain polymers and inorganic particles at the interface during capsule manufacturing, and then a reactive substance or a dispersed phase including a reactive substance and an active ingredient is mixed using this By forming a pickering emulsion and allowing polymerization of the outer wall reinforcing material and the reactive material to proceed at the interface, there is a feature of providing an organic-inorganic hybrid microcapsule that has few toxic substances and exhibits high versatility and economy.

In addition, since inorganic particles are included in the outer wall of the capsule, the hardness and elasticity of the outer wall can be controlled, and a capsule capable of easily expressing the activity of the active ingredient can be prepared.

In addition, the present invention can prepare an eco-friendly organic-inorganic hybrid capsule when a natural polymer, its derivatives, and natural polymers are used as precursors.

At this time, the method of manufacturing the microcapsules of the present invention can be carried out largely over three steps.

The first step is a step of first preparing a continuous phase in order to form a pickering emulsion to be described later.

The continuous phase may contain a reactive material that is a precursor of a material for the outer wall of the capsule that is generated in the encapsulation process in the future. The continuous phase refers to a material maintained in a liquid state at room temperature, and may mean a solution including at least one of solvents generally used in a process.

In addition, the continuous phase may include a first solution of a continuous phase containing inorganic particles and a second solution of a continuous phase containing a polymer material.

Preferably, the first solution in the continuous phase contains inorganic particles as a precursor of the material for the outer wall of the capsule, and the second solution in the continuous phase may contain a polymer precursor for reinforcing the outer wall.

The inorganic particles serve as pickering particles that increase the stability of the dispersion phase in the future interfacial polymerization process, and are mixed in the polymer polymerization process to increase the hardness and lower the elasticity of the capsule outer wall.

The inorganic particles may contain 0.001 to 30% by weight based on the total weight of the first solution in the continuous phase. The inorganic particles contained in the first solution are 0.001 parts by weight to 100 parts by weight, preferably 0.005 parts by weight to 75 parts by weight, more preferably, based on the total weight of the dispersed solution. It may be 0.01 parts by weight to 50 parts by weight. If the content of the inorganic particles is 0.001 parts by weight or less (0.001 wt% or less based on the first solution), there is a problem that pickering emulsion cannot be formed, and if the content is 100 parts by weight or more (30 wt% or more based on the first solution), a gel is formed and the viscosity There is a problem that increases.

The inorganic particles may have a diameter of 1 nm or more and 900 nm or less, preferably 1.5 nm or more and 750 nm or less, and more preferably 2 nm or more and 500 nm or less.

The inorganic particles are from the group consisting of haloysite nanotubes, laponite, kaolinite clay, colloidal silica, calcium hydroxide, magnesium hydroxide, magnesium oxide, alumina, aluminum hydroxide, aluminum phosphate, calcium pyrrolate, aluminum pyrrolate, and zinc pyrrolate. It may be one or more selected.

Meanwhile, the first step may further include a step of surface treatment of the inorganic particles.

The contact angle θ used to define the characteristics of the inorganic particles may be defined as shown in FIG. 1. As shown in FIG. 1, after drawing a tangent line at the point where inorganic particles located at the horizontal interface of the continuous phase and the dispersed phase meet the interface, the angle formed by the tangent line and the interface in the continuous phase is referred to as a contact angle.

When the inorganic particles exist in the continuous phase and the dispersed phase, the contact angle is 90 degrees or less. For these inorganic particles, it is possible to control the inorganic particles to serve as pickering particles through surface treatment.

Accordingly, the first step may further include a surface treatment step of allowing the inorganic particles to have a contact angle of 90 degrees or less between the continuous phase and the dispersed phase. Through the surface treatment, the contact angle of the inorganic particles may be 0 degrees or more and 90 degrees or less, preferably 5 degrees or more and 90 degrees or less, and more preferably 10 degrees or more and 90 degrees or less.

The surface treatment step may be performed, including the step of adding a surface treatment material for adjusting the contact angle of the inorganic particles to the continuous first solution containing the inorganic particles.

The surface treatment material is a non-covalent surface treatment material such as cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, distearyldimonium chloride, aluminum stearate, and the like, Covalently bonded surface treatment materials such as halosilane-based materials, alkoxysilane and derivatives thereof are included, and at least one selected from the above materials may be used.

In addition, the first solution of the continuous phase may contain distilled water as a residual amount of solvent in addition to inorganic particles. The distilled water may be purified and used according to a method well known in the art.

On the other hand, the second solution in the continuous phase contains the polymer precursor 1 for reinforcing the outer wall. The polymer precursor 1 refers to a material for reinforcing the outer wall contained in the continuous phase, which is soluble in the continuous phase and refers to a material that forms the outer wall of the capsule by reacting with the reactive material in the future.

The polymer precursor 1 may contain 0.001 to 20% by weight based on the total weight of the second solution in the continuous phase. The polymer precursor 1 for reinforcing the outer wall may be 0.002 to 30 parts by weight, preferably 0.006 to 25 parts by weight, more preferably 0.011 to 20 parts by weight, based on the total weight of the dispersed solution. have. If the content of the polymer precursor 1 is 0.002 parts by weight or less (0.001 wt% or less based on the second solution), there is a problem that the capsule is not formed, and if the content of the polymer precursor 1 is more than 30 parts by weight ((20 wt% or more based on the second solution), non-uniform reaction There is a problem that the stability of the capsule is poor.

The polymer precursor 1 for reinforcing the outer wall of the capsule includes a precursor capable of forming a polymer such as polyamide, polyurethane, polyurea, and polyester.

As a representative example, the polymer precursor 1 may be one or more selected from the group consisting of a compound having two or more amine groups, a compound having two or more hydroxy groups, and a natural polymer.

For a preferred example, the compound having two or more amine groups may include a compound represented by Formula 1 below.

[Formula 1]

(In Formula 1,

Each of R ₁ is independently and at the same time one or more amine groups or one or more heteroatoms or not, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or alkylene having 1 to 50 carbon atoms and carbon number It may contain 3 to 60 cyclic hydrocarbon groups,

n is an integer from 1 to 5000)

In the present invention, the cyclic hydrocarbons having 3 to 30 carbon atoms may each independently and at the same time contain one or more amine groups or one or more heteroatoms or not, cyclic saturated or unsaturated hydrocarbons (aromatic hydrocarbons).

More specifically, the compound having two or more amine groups is methylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris( 2-aminoethyl)amine (tris(2-aminoethyl)amine), polyethyleneimine, poly(propylene glycol) bis(2-aminopropyl ether) (Poly(propylene glycol) bis(2-aminopropyl ether)), Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether, poly(ethylene glycol) bis(amine)) (Poly(ethylene glycol) bis (amine)), o-Phenylenediamine, p-Phenylenediamine, m-Phenylenediamine, 2,4-diaminotoluene (2,4- Diaminotoluene), 2,3-Diaminotoluene (2,3-Diaminotoluene), 2,5-diaminotoluene (2,5-Diaminotoluene), 3,3'-diaminodiphenylmethane (3,3'-Diaminodiphenylmethane) ), 3,4'-diaminodiphenylmethane (3,4'-Diaminodiphenylmethane), 4,4'-diaminodiphenylmethane (4,4'-Diaminodiphenylmethane), 4,4'-ethylenedianiline (4 ,4'-Ethylenedianiline), 4,4'-diaminodiphenyl sulfide (4,4'-Diaminodiphenyl sulfide), 4,4'-oxydianiline (4,4'-Oxydianiline), Pararosaniline base (Pararosaniline) Base), melamine and tetrakis (4-amid One or more selected from the group consisting of nophenyl) methane (Tetrakis (4-aminophenyl) methane) may be used.

The compound having two or more hydroxy groups may include a compound represented by Formula 2 below.

[Formula 2]

(In Chemical Formula 2,

R ₂ is each independently and at the same time, having or not having at least one hydroxy group or at least one hetero atom, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or alkylene having 1 to 50 carbon atoms and 3 carbon atoms It may contain a cyclic hydrocarbon group of to 60,

n is an integer from 1 to 5000)

More specifically, the compound having two or more hydroxy groups is methanediol, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, Heptanediol, Octanediol, Nonanediol, Decanediol, Dodecanediol, Tetradecanediol, Hexadecanediol, Ethylene Glycol (Ethy glycolelen) ), Threitol, Ribitol, Galactitol, Fucitol, Iditol, Inositol, Volemitol, Maltotriitol , Maltotetraitol, Polyglycitol, Arabitol, Erythritol, Glycerol, Isomalt, Lactitol, Maltitol, Mannitol (Mannitol), Sorbitol, Xylitol, Sucrose, Polyethylene glycol, Polypropylene glycol, Polyvinyl alcohol, VP/vinyl alcohol copolymer (VP/Vinyl alcohol copolymer), Butendiol/Vinyl Alcohol Copolymer, Polyglycerin, Glyceryl Polyacrylate, Dimethiconol, Bis-hydroxy Ethoxypropyl Dimethicone (Bis-Hydroxyethoxypropyl Dimethicone), Bis-Hydroxypropyl Dimethicone Methicone (Bis-Hydroxypropyl Dimethicone), hydroxypropyl dimethicone (Hydroxypropyldimethicone), and bis-hydroxyethyl tromethamine (Bis-Hydroxyethyl Tromethamine) at least one selected from the group consisting of may be used.

In addition, in the present invention, as a polymer precursor capable of interfacial polymerization for the production of eco-friendly capsules, at least one selected from the group consisting of natural polymers, derivatives thereof, and polymers using naturally derived components may be used. Examples of the natural polymer include gelatin, chitosan, polylysine, and the like as a substance containing two or more amine groups.

In addition, the second solution in the continuous phase may contain distilled water as a residual amount of solvent in addition to the polymer precursor 1. The distilled water may be purified and used according to a method well known in the art.

Meanwhile, the second step is a step of preparing a dispersed phase for mixing with the continuous phase.

The dispersed phase contains a specific reactive substance or a reactive component and an active ingredient that are precursors of the capsule outer wall material generated in the future encapsulation process. The dispersed phase refers to a substance that is maintained in a liquid state at room temperature, and generally refers to one or more of the solvents used in the process. When the active ingredient is a liquid at room temperature, the active ingredient may be used as the dispersed phase.

In addition, the dispersed phase refers to a solvent that is not mixed with the continuous phase. Typically, when the continuous phase is water, the dispersed phase is a hydrocarbon-based solvent having a linear or nonlinear structure such as pentane, hexane cyclohexane, heptane, octane, isododecane, and dodecane, ethers such as ethyl ether, butyl ether, and methyl-t-butyl ether. Its derivative-based solvent containing a group, its derivative-based solvent containing an ester group such as ethyl acetate, butyl acetate, and ethyl butyrate, a ketone-based solvent such as methyl ethyl ketone, an aromatic solvent such as benzene, toluene, and xylene, dichloromethane, There are haloalkane-based solvents such as dichloroethane, chloroform, and carbon tetrachloride, and silicone-based solvents such as dimethicone and cyclomethicone, and these may be used by selecting one or more.

In addition, the solvent applicable to the above-mentioned dispersion phase can be applied in a continuous phase as necessary.

In the dispersion phase solution, the solvent content may be included in the remaining amount, and may be appropriately adjusted according to the added component.

A reactive material that is a precursor of a material for the outer wall of the capsule contained in the dispersed phase is included. The reactive material is a material that can form the outer wall of the capsule by reacting with the outer wall reinforcing material dissolved in the continuous phase, and is a material that is well soluble in the dispersed phase.

This reactive material is referred to as polymer precursor 2 in the present invention. The polymer precursor 2 includes a precursor of polymer materials capable of interfacially reacting with the polymer precursor 1 for reinforcing the outer wall to form poly(β-amino ester).

According to a preferred embodiment, the polymer precursor 2 may include at least one selected from the group consisting of a compound having two or more acrylate structures represented by the following formula (3).

[Chemical Formula 3]

(In Chemical Formula 3,

Each of R ₃ is independently and at the same time one or more acrylates or one or more heteroatoms or not, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or alkylene having 1 to 50 carbon atoms and carbon number It may contain 3 to 60 cyclic hydrocarbon groups)

More specifically, the compound having two or more acrylate groups is ethylene glycol diacrylate, di (ethylene glycol) diacrylate (Di (ethylene glycol) diacrylate), tri (ethylene glycol) diacrylate ( Tri(ethylene glycol) diacrylate), Tetra(ethylene glycol) diacrylate, Poly(ethylene glycol) diacrylate), Propylene glycol diacrylate diacrylate), di (propylene glycol) diacrylate, tri (propylene glycol) diacrylate (Tri (propylene glycol) diacrylate), tetra (propylene glycol) diacrylate (Tetra (propylene glycol) diacrylate) ) diacrylate), poly(propylene glycol) diacrylate, butanediol diacrylate, hexanediol diacrylate, hexanediol ethoxylate diacrylate (Hexanediol ethoxylate diacrylate), neopentyl glycol propoxylate (1 PO/OH) diacrylate), trimethylolpropane ethoxylate (1 EO/OH) methyl ether diacrylate ( Trimethylolpropane ethoxylate (1 EO/OH) methyl ether diacrylate), Neopentyl glycol diacrylate, Pentaerythritol triacrylate, Trimethylolpropane triacrylate pane triacrylate), trimethylolpropane propoxylate triacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate (Tris[2-(acryloyloxy)ethyl] isocyanurate), trimethylol Propane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, hydroxypivalyl hydroxypivalate bis[ At least one selected from the group consisting of 6-(acryloyloxy)hexanoate] (Hydroxypivalyl hydroxypivalate bis[6-(acryloyloxy)hexanoate]) may be used.

The polymer precursor 2 may contain 0.001 to 30% by weight, preferably 0.005 to 25% by weight, and more preferably 0.01 to 20% by weight, based on the total weight of the dispersed phase solution. If the content of the polymer precursor 2 is 0.001% by weight or less, there is a problem that the capsule is not formed, and if the content of the polymer precursor 2 is more than 30% by weight, there is a problem that the stability of the capsule is deteriorated due to a non-uniform reaction.

The active ingredient is a substance that is desired to maintain its activity by the resulting capsule, and is a substance whose activity is expressed as the outer wall is destroyed later. When the active ingredient is a liquid at room temperature, it may replace the dispersed phase, which is a solvent, otherwise it may vary depending on the solubility. Examples of the active ingredient may include fragrances, dyes, catalysts, antioxidants, drugs, and the like, and one or more types may be selected and used.

Even if the active ingredient is contained in a small amount, its properties may be expressed, and since it may itself become a dispersed phase, up to 100 parts by weight based on 100 parts by weight of the dispersed phase solution may be included as needed. Therefore, the content of the active ingredient is not greatly limited, and the content may be set according to the ingredient material used, and may be used according to what is known in the art.

In addition, the present invention provides a step for forming at least one polymer selected from the group consisting of polyamide, polyurethane, polyurea and polyester, in addition to poly(β-amino ester), which is a biodegradable polymer, in order to increase capsule stability. It may contain more.

For example, when preparing the dispersion phase solution, at least one polymer precursor 3 selected from the group consisting of a compound containing two or more acid chloride structures, a compound containing two or more isocyanate structures, and a compound containing two or more chloroformate structures It may further include.

The compound containing two or more acid chloride structures may be a compound represented by the following formula (4).

[Formula 4]

(In Chemical Formula 4,

R ₄ are each independently and at the same time one or more acid chloride (-COCl) or alkylene having 1 to 50 carbon atoms, having or not having one or more hetero atoms, a cyclic hydrocarbon group having 3 to 60 carbon atoms, or a carbon number of 1 to 50 Alkylene and a cyclic hydrocarbon group having 3 to 60 carbon atoms)

The compound containing two or more isocyanate structures may be a compound represented by the following formula (5).

[Formula 5]

(In Chemical Formula 5,

R ₅ are each independently and at the same time having or not having at least one isocyanate or at least one hetero atom, an alkylene having 1 to 50 carbon atoms, a cyclic hydrocarbon group having 3 to 60 carbon atoms, or an alkylene having 1 to 50 carbon atoms and 3 carbon atoms. To 60 cyclic hydrocarbon groups)

The compound containing two or more chloroformate structures may be a compound represented by the following formula (6).

[Formula 6]

(In Chemical Formula 6,

R ₆ are each independently and at the same time one or more chloroformate (-OCOCl) or alkylene having 1 to 50 carbon atoms, having or not having one or more hetero atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or 1 to 50 carbon atoms May include an alkylene and a cyclic hydrocarbon group having 3 to 60 carbon atoms)

More specifically, the compound having two or more acid chlorides is malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, pimeloyl chloride (Pimeloyl chloride), Suberoyl chloride (Suberoyl chloride), Sebacoyl chloride (Sebacoyl chloride), Azelaic acid dichloride (Azelaic acid dichloride) and at least one selected from the group consisting of Dodecanedioyl dichloride (Dodecanedioyl dichloride) Can be used.

More specifically, the compound having two or more isocyanates is methylene diisocyanate, 1,4-phenylene diisocyanate, and tolylene-2,4-diisocyanate. ,4-diisocyanate), 1-chloromethyl-2,4-diisocyanatobenzene, 4-chloro-6-methyl-1,3-phenylene diisocyanate (4 -Chloro-6-methyl-1,3-phenylene diisocyanate), 1,3-bis(1-isocyanato-1-methylethyl)benzene (1,3-Bis(1-isocyanato-1-methylethyl)benzene ), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (3,3'-Dimethyl-4,4'-biphenylene diisocyanate), 3,3'-dichloro-4,4'-diisocy Anato-1,1'-biphenyl (3,3'-Dichloro-4,4'-diisocyanato-1,1'-biphenyl), 4,4'-oxybis (phenyl isocyanate) (4,4'- Oxybis (phenyl isocyanate)), 4,4'-methylenebis (phenyl isocyanate) (4,4'-Methylenebis (phenyl isocyanate)), 4,4'-methylenebis (2,6-diethylenephenyl isocyanate) (4 ,4'-Methylenebis(2,6-diethylphenyl isocyanate)), isoprene diisocyanate, trans-1,4-cyclohexylene diisocyanate (trans-1,4-Cyclohexylene diisocyanate), 1,3-bis (Isocyanatomethyl) cyclohexane (1,3-Bis (isocyanatomethyl) cyclohexane), 4,4'-methylenebis (cyclohexyl isocyanate) (4,4'-Methylenebis (cyclohexyl isocyanate)), diisocyanato Butane (Diisocyanatobutane), hexamethylene di Isocyanate (Hexamethylene diisocyanate), Diisocyanatooctane, Diisocyanatododecane and 1,6-diisocyanato-2,2,4-trimethylhexane (1,6-Diisocyanato-2, 2,4-trimethylhexane) may be used.

More specifically, the compound having two or more chloroformates is ethylenebis (chloroformate), diglycolyl chloride, oxydiethylene bis (chloroformate) (oxydiethylene bis ( chloroformate)), tri(ethylene glycol) bis(chloroformate) (Tri(ethylene glycol) bis(chloroformate)), 1,4-phenylene bis(chloroformate) (1,4-Phenylene bis(chloroformate)) , Bisphenol A bis (chloroformate) (Bisphenol A bis (chloroformate)) and bisphenol Z bis (chloroformate) (Bisphenol Z bis (chloroformate)) at least one selected from the group consisting of may be used.

Meanwhile, the third step is a step of preparing a biodegradable organic-inorganic hybrid microcapsule by forming a pickering emulsion using a continuous phase solution and a dispersed phase solution, and then performing interfacial polymerization.

Specifically, as shown in Fig. 2, the microcapsules of the present invention form a pickering emulsion after mixing the continuous phase and the dispersed phase solution, and are formed through interfacial polymerization. Polymers and inorganic particles, which are materials for the outer wall of the capsule, are present at the interface.

More preferably, the first solution in the continuous phase and the solution in the dispersed phase are mixed to form a Pickering emulsion, and then a second solution in the continuous phase is added thereto, and interfacial polymerization is performed to form microcapsules.

In the third step, when the pickering emulsion is formed by mixing the continuous first solution and the dispersed solution, the stirring conditions are 10 or more and 16000 RPM or less, preferably 50 or more and 13000 RPM or less, and more preferably 100 or more and 10000. It may be less than RPM.

In addition, the interfacial polymerization reaction after the addition of the second solution in the continuous phase proceeds at 0 to 100°C for 1 to 48 hours, preferably at 10 to 90°C for 2 to 24 hours, and more preferably Can proceed for 3 to 12 hours at 20 to 80 °C. At this time, the stirring conditions may be 10 or more and 6000 RPM or less at room temperature, preferably 50 or more and 5000 RPM or less, and more preferably 100 or more and 4000 RPM or less.

If necessary, the method of the present invention may further include the step of introducing a dispersion stabilizer in the capsule manufacturing process. Specifically, the dispersion stabilizer may be used when forming the outer wall of the capsule.

According to a preferred embodiment, the method of the present invention may further include the step of adding a dispersion stabilizer in the first step or the third step.

The dispersion stabilizer may be used for the purpose of increasing the dispersibility of the capsule produced after the reaction. As the dispersion stabilizer, gum arabic, polysaccharide, pectin, alginate, arabinogalactan, carrageenan, gellan gum, xanthan gum, guar gum, acrylate/acrylic polymer, starch, water-swellable clay, acrylate/aminoacrylate Copolymers, and mixtures thereof, maltodextrin; Natural gums such as alginate esters; Gelatin, protein hydrolysates and quaternized forms thereof; Synthetic polymers and copolymers such as poly(vinyl pyrrolidone-co-vinyl acetate), poly(vinyl alcohol-co-vinyl acetate), poly(maleic acid), poly(alkylene oxide), poly(vinylmethyl) Ether), poly(vinylether-co-maleic anhydride), etc., as well as poly(ethyleneimine), poly((meth)acrylamide), poly(alkyleneoxide-co-dimethylsiloxane), poly(aminodimethyl Siloxane) and the like may be used.

The amount of the dispersion stabilizer can be used within a range well known in the art.

After the polymerization in the third step, if necessary, a step of concentrating or/and drying the solution containing microcapsules may be further included, and the conditions are not limited thereto.

In addition, in the present invention, the pH can be adjusted using an acid or a basic substance, and the conditions are not limited.

On the other hand, according to another embodiment of the present invention, a capsule according to the method, comprising a dispersion phase positioned in a core and an outer wall of a hybrid capsule surrounding the outside of the dispersion phase, and a dispersion phase of 1 to 90% by weight based on the total weight of the capsule Including, organic-inorganic hybrid microcapsules may be provided.

Specifically, in the organic-inorganic hybrid microcapsule of the present invention, as shown in FIG. 2, a dispersed phase is located in a core, and an organic-inorganic hybrid outer wall formed by interfacial polymerization is formed outside the dispersed phase.

Preferably, the microcapsules are dispersed phase; And an outer wall of a hybrid capsule including poly(β-amino ester) and inorganic particles formed at the interface of the dispersed phase.

Here, the poly(β-amino ester) polymer is formed by a reaction between the outer wall reinforcing material and the reactive material as described above, and may be selectively formed using a catalyst. In this case, the catalyst may be included on the outer wall of the final capsule structure.

In addition, since inorganic particles are included in the interfacial polymerization process, cracking is improved by controlling the hardness and elasticity of the outer wall of the capsule.

In addition, the biodegradable organic-inorganic hybrid microcapsule may include a dispersed phase of 1 to 90% by weight relative to the total weight of the capsule, preferably 3 to 85% by weight, more preferably 5 to 80% by weight of the dispersed phase. can do.

The outer wall of the organic-inorganic hybrid capsule polymerized and included at the interface of the microcapsule can be adjusted in strength compared to the conventional one, so that the activity of the active ingredient can be easily expressed. In particular, the organic-inorganic hybrid capsule of the present invention exhibits a range of strength suitable for product application, for example, may exhibit a strength of about 50 to 200 MPa or about 50 to 160 MPa, and it is easy to adjust the strength within the above range when the product is applied. There is one advantage.

In addition, the average particle diameter of the microcapsules of the present invention may be 0.1 μm or more and 1000 μm or less.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention, and the scope of the invention is not limited to any meaning.

<Example>

In the present invention, the capsule strength and size were evaluated by the following method.

(1) strength

The strength of the capsule was measured using a Nanoindentation test device (CMS instrument). At this time, the strength was obtained by dividing the maximum load value by the contact area.

(2) size

The size of the capsule was measured using a Malvern Mastersizer 3000.

[Experimental Example 1] Comparison of capsule strength to which various inorganic particle materials are applied

In order to prescribe and use microcapsules in products, an appropriate strength is required. If the strength of microcapsules is too high, there is a problem that it is difficult to apply to products, so it is important to control the strength. Accordingly, strength comparison experiments were conducted for the conventional general organic microcapsules and the organic-inorganic hybrid microcapsules according to the method of the present invention.

To this end, the organic microcapsules of Comparative Example 1 and the inorganic particle material-based, biodegradable organic-inorganic hybrid capsules of Examples 1 to 5 were prepared by the following method, and then, strength and size of each capsule were measured. The measurement results are shown in Table 1.

Comparative Example 1

Step 1

0.15 g of sodium dodecyl sulfate was dispersed in 59.85 g of distilled water to prepare a continuous phase 1 (first solution). In addition, 1 g of polyethyleneimine was added to 9 g of distilled water and mixed to prepare a continuous phase 2 (second solution).

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of dodecane and mixed to prepare a dispersed phase.

Step 3

Under 2000RPM conditions, the dispersion phase solution was gradually added to the continuous phase 1 (first solution) and stirred to prepare an emulsion. Thereafter, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 (second solution) was added to the emulsion, and interfacial polymerization was conducted at 80° C. for 12 hours to prepare a poly(β-amino ester) microcapsule.

Examples 1 to 5

Step 1

Inorganic particles (Silica, Laponite, Iron oxide, Alumina, Titanium oxide) were each dispersed in 59 g of distilled water to prepare a continuous phase 1 (first solution). In addition, 1 g of polyethyleneimine was added to 9 g of distilled water to prepare a continuous phase 2 (second solution).

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of dodecane and mixed to prepare a dispersed phase.

Step 3

Under the conditions of 2000RPM, the dispersion phase solution was gradually added to the continuous phase 1 (first solution) and stirred to prepare a Pickering emulsion. After that, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 (second solution) was added to the Pickering emulsion and interfacial polymerization was conducted at 80° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsule.

Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Distilled Water 68.85 68 68 68 68 68 Silica - One - - - - Laponite - - One - - - Iron oxide - - - One - - Alumina - - - - One - Titanium oxide - - - - - One Sodium dodecyl Sulfate 0.15 - - - - - 1,6-Hexanediol diacrylate 0.5 0.5 0.5 0.5 0.5 0.5 Polyethyleneimine One One One One One One Dodecane 29.5 29.5 29.5 29.5 29.5 29.5 Strength (MPa) 443.1 65.7 78.3 56.3 80.9 65.4 Size (μm) 27.1 17.5 15.9 23.4 19.6 18.2

From the results of Table 1, the organic microcapsules of Comparative Example 1 had too high strength, such as 443.1 MPa, so that it was difficult to apply to a product, and strength control was also difficult.

On the other hand, the organic-inorganic hybrid microcapsules of Examples 1 to 5 of the present invention were similar in size, and could be made with a strength suitable for use in products of about 56.3 to 80.9 MPa. In addition, Examples 1 to 5 showed the advantage of easy strength control to improve workability and usability.

[Experimental Example 2] Capsule strength control

After preparing the capsules of Examples 6 to 9 in which the polymer content was decreased or increased compared to Example 1 in the following manner, the capsule strength and size were measured for each capsule. The measurement results are shown in Table 3.

Examples 6 to 9

Step 1

1 g of silica was dispersed in 59 g of distilled water, respectively, to prepare a continuous phase 1 (first solution). In addition, polyethyleneimine was added to distilled water according to the contents disclosed in Table 3 to prepare a continuous phase 2 (second solution).

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of dodecane and mixed to prepare a dispersed phase.

Step 3

Under the conditions of 2000RPM, the dispersion phase solution was gradually added to the continuous phase 1 (first solution) and stirred to prepare a Pickering emulsion. Thereafter, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 (second solution) was added to the pickering emulsion and interfacial polymerization was conducted at 80° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsule.

Example 6 Example 7 Example 1 Example 8 Example 9 Distilled Water 68.75 68.5 68.0 67.5 67.0 Silica One One One One One 1,6-Hexanediol diacrylate 0.125 0.25 0.5 0.75 One Polyethyleneimine 0.25 0.5 One 1.5 2 Dodecane 29.875 29.75 29.5 29.25 29 Strength (MPa) 31.1 53.4 65.7 109.3 155.9 Size (μm) 38.8 27.4 17.5 13.1 11.5

From the results of Table 2, the present invention was able to adjust the capsule strength according to the polymer content, and in the case of Examples 8 and 9, as the content of 1,6-hexanediol diacrylate and polyethyleneimine increased compared to Example 1 , It was confirmed that the strength of the capsule became stronger.

Accordingly, the present invention can provide a variety of organic-inorganic hybrid microcapsules capable of adjusting the capsule strength.

[Experimental Example 3] Release behavior of volatile oil

After preparing the microcapsules of Comparative Example 2 by the following method, the strength and size were measured, and the results are shown in Table 3.

In addition, with respect to Comparative Example 1, Comparative Example 2, Example 1, and Examples 7 to 9, the discharge behavior of the volatile oil in the dispersed phase was compared.

As a method of measuring the release behavior of volatile oil, the mass change was measured at 120° C. for 4 hours, and measured using MA-100 from Satorius, and the results are shown in Table 4 and FIG. 3 below.

Comparative Example 2

Step 1

After treating the silica surface with 25% CTAC (Cetyltrimethyl ammonium chloride), it was dispersed in distilled water to prepare a continuous phase.

Step 2

A dispersed phase was prepared by adding 3 g of TEOS to 30 g of dodecane.

Step 3

Under 2000RPM conditions, the dispersion phase was slowly added to the continuous phase and stirred to prepare a Pickering emulsion. Thereafter, the pH of the emulsion was adjusted to 10 using NaOH, and interfacial polymerization was performed at 25° C. for 12 hours to prepare a silica-based microcapsule.

Comparative Example 5 Distilled Water 61 Silica 2 25% CTAC 4 TEOS 3 Dodecane 30 Strength (MPa) 12.4 Size (μm) 36.1

Comparative Example 1 Comparative Example 2 Example 6 Example 7 Example 1 Example 8 Example 9 After final drying
Balance(%) 33.5 4.3 4.6 8.8 16.3 21.5 26.4

From the results of Table 4 and FIG. 3, it was confirmed that the internally dispersed phase was gradually released in Examples 7 to 9 over time.

[Experimental Example 4] Flavor Capsule Preparation and Washing Evaluation

After preparing each flavor capsule of Comparative Examples 3 to 4 and Example 10 as follows as an actual application example, strength and size were measured, and laundry evaluation was also conducted.

That is, it was thought that the biodegradable organic-inorganic hybrid capsule of Example would exhibit high scent odor due to the excellent expression and crackability of the active ingredient, and to verify this, two comparative examples and one example were prepared, and strength Was measured and the washing evaluation was performed.

As for the fragrance oil, commercially available oil was used. In addition, conventionally known polyurea, polyamide, polyurethane, polyester, melamine-formaldehyde resin capsules were set as Comparative Examples 3 to 4.

1) Strength and size: It was measured according to the method described above.

2) laundry evaluation

As the test fiber, a commercially available cotton towel (30 X 20 cm) was prepared, and then a standard amount of general laundry detergent was used, and the fiber was repeatedly washed 5 times in a washing machine and then dehydrated. Each microcapsule of Comparative Examples and Examples was made into a 1% aqueous solution, and then the standard used amount (0.67 ml/1 l washing water) was quantified in a stirred washing machine and treated with a rinsing course, and the cotton towel was taken out after dehydration. . And the cotton towel was dried for 12 hours at a humidity of 30% and a temperature of 25 ℃.

At this time, three time points (right after washing, after drying, after rubbing) were set, and 20 experienced Panelists conducted sensory evaluation to evaluate the fragrance intensity. The fragrance intensity was given from the lowest point 0 to the highest point 5 points based on the capsule-free cotton towel, and this was repeated three or more times to perform reverberation evaluation with the average value. The results are shown in Table 5 and FIG. 4.

Comparative Example 3

Step 1

0.15 g of sodium dodecyl sulfate was dispersed in 59.85 g of distilled water to prepare a continuous phase 1 (first solution). In addition, 1 g of polyethyleneimine was added to 9 g of distilled water to prepare a continuous phase 2 (second solution).

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of perfume and mixed to prepare a dispersed phase.

Step 3

-amino ester) 마이크로 캡슐을 제조하였다.Under the conditions of 2000 RPM, the dispersion phase was slowly added to the continuous phase 1 (first solution) and stirred to prepare an emulsion. After that, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 (second solution) was added to the emulsion, and interfacial polymerization was carried out at 80°C for 12 hours, and Poly(

-amino ester) microcapsules were prepared.

Comparative Example 4

Step 1

Sodium dodecyl sulfate, Tween 20, Arabic gum, and pre-melamine formaldehyde solution were dispersed in 54 g of distilled water to prepare a continuous phase.

Step 2

Under the conditions of 2000RPM, 30 g of perfume (dispersion phase) was gradually added to the continuous phase to prepare an emulsion.

Step 3

After lowering the speed of the stirrer to 1000 RPM, the pH was lowered to 5 with citric acid, and the capsule formation reaction was performed at 70° C. for 3 hours. After terminating the reaction by adjusting the pH to 7.5 using tromethamine, a melamine-formaldehyde resin capsule was prepared.

Example 10

Step 1

1 g of silica was dispersed in 59 g of distilled water to prepare a continuous phase 1 (first solution). In addition, 1 g of polyethyleneimine was added to 9 g of distilled water to prepare a continuous phase 2 (second solution).

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of perfume and mixed to prepare a dispersed phase.

Step 3

Under 2000RPM conditions, the dispersion phase was slowly added to the continuous phase 1 (first solution) and stirred to prepare a Pickering emulsion. Thereafter, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 (second solution) was added to the Pickering emulsion and interfacial polymerization was performed at 80° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsule.

Comparative Example 3 Comparative Example 4 Example 10 Immediately after washing 0.97 1.07 3.15 after drying 1.34 1.25 3.88 After rubbing 1.91 2.34 4.47

Looking at the results of Tables 5 and 4, it was confirmed that Example 10 of the present invention had excellent scent odor in laundry evaluation compared to Comparative Examples 3 to 4.

[Experimental Example 5] Evaluation of biodegradability of flavor capsules

In this experimental example, after preparing Example 11 by the following method, the outer wall material of the fragrance capsule of the present invention was separated to evaluate and compare the biodegradability.

Example 11 Distilled Water 68 Silica One 1,6-Hexanediol diacrylate 0.5 Chitosan One Spices 29.5 Strength (MPa) 50.1 Size (μm) 20.4

Example 11

Step 1

1 g of silica was dispersed in 59 g of distilled water to prepare a continuous phase 1. In addition, 1 g of chitosan was added to 9 g of distilled water to prepare continuous phase 2.

Step 2

0.5 g of 1,6-hexanediol diacrylate was added to 29.5 g of perfume and mixed to prepare a dispersed phase.

Step 3

Under the conditions of 2000RPM, the dispersion phase was slowly added to the continuous phase 1 and stirred to prepare a Pickering emulsion. Thereafter, after lowering the speed of the stirrer to 1000 RPM, continuous phase 2 was added to the Pickering emulsion and interfacial polymerization was performed at 80° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsule.

Separation of the outer wall material of the capsule

First, the outer wall material of the capsule and the core oil (fragrance oil) were separated. The composition of the present invention (Comparative Examples 4 and 10, 11) was first dispersed in ethanol, and then only the outer wall material of the capsule was separated using a centrifuge. Thereafter, the core oil (fragrance oil) was removed with ethanol three more times in the same manner, and then dried at 60° C. for 24 h with a vacuum pump.

Biodegradability measurement

Biodegradability was measured according to the generally well-known OECD 301 F method, after measuring COD (Chemical Oxygen Demand) and BOD (Biochemical Oxygen Demand), and then based on the following calculation method.

COD measurement was measured according to the ISO 6060 method. Briefly, an appropriate amount of a sample was oxidized with sulfuric acid and an excess of potassium dichromate, and the remaining potassium dichromate was titrated using FAS (Ferrous ammonium sulfate), and COD was calculated from the number of moles of dichromate used in the oxidation reaction.

To measure BOD, an aqueous solution containing microorganisms was prepared according to the method specified in OECD 301, and an appropriate amount of sample (0.1g or more per liter) was added, and oxygen consumption was measured with a respirometer for 28 days. At this time, a potassium hydroxide solution was used to remove carbon dioxide generated by microorganisms, and a blank solution containing no samples was simultaneously measured, and BOD was calculated through Equation 1 below.

[Equation 1]

The degree of biodegradation was obtained using the following equation 2.

[Equation 2]

Comparative Example 4 Example 10 Example 11 Biodegradability (%) 10.4 62.9 86.2

As shown in Table 7, Example 10 of the present invention showed excellent biodegradability compared to Comparative Example 3, and Example 11 using a natural polymer confirmed a more excellent biodegradability.

Claims (15)

A first step of preparing a continuous first solution containing inorganic particles and a second continuous solution containing a polymer precursor 1 for strengthening the outer wall;
A second step of preparing a biodegradable polymer precursor 2 reacting with the polymer precursor 1 for reinforcing the outer wall, or a dispersion phase solution including an active ingredient and the polymer precursor 2; And
A third step of forming a pickering emulsion by adding a dispersion phase solution to the first solution, and then forming the outer wall of the capsule by interfacial polymerization by adding a second solution, and
The outer wall of the capsule contains poly(β-amino ester) and inorganic particles,
The outer wall reinforcing polymer precursor 1 and the biodegradable polymer precursor 2 each independently contain one or more precursors for forming poly(β-amino ester),
The strength is characterized in that 50 to 200 MPa or less,
Method for producing biodegradable organic-inorganic hybrid microcapsules.
The method of claim 1,
The polymer precursor 1 is at least one selected from the group consisting of a compound having two or more amine groups represented by the following formula (1), a compound having two or more hydroxy groups represented by the following formula (2), and a natural polymer,
Method for producing biodegradable organic-inorganic hybrid microcapsules.
[Formula 1]

(In Formula 1,
Each of R ₁ is independently and at the same time one or more amine groups or one or more heteroatoms or not, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or alkylene having 1 to 50 carbon atoms and carbon number It may contain 3 to 60 cyclic hydrocarbon groups,
n is an integer from 1 to 5000)
[Formula 2]

(In Chemical Formula 2,
R ₂ are each independently and at the same time, having or not having at least one hydroxy group or at least one hetero atom, an alkylene having 1 to 50 carbon atoms, a cyclic hydrocarbon group having 3 to 60 carbon atoms, or an alkylene having 1 to 50 carbon atoms and 3 carbon atoms. It may contain a cyclic hydrocarbon group of to 60,
n is an integer from 1 to 5000)
The method of claim 2,
Compounds having two or more amine groups include methylenediamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, tris(2-aminoethyl)amine, polyethyleneimine, poly(propylene glycol) bis(2- Aminopropyl ether, trimethylolpropane tris[poly(propylene glycol), amine terminated] ether, poly(ethylene glycol) bis(amine), o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,3-diaminotoluene, 2,5-diaminotoluene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenylmethane, 4,4'-ethylenedianiline, 4,4'-diaminodiphenyl sulfide, 4,4'-oxydianiline, pararosaniline base, melamine and tetrakis (4-aminophenyl ) Method for producing a biodegradable organic-inorganic hybrid microcapsule that is at least one selected from the group consisting of methane.
The method of claim 2, wherein the natural polymer is at least one selected from the group consisting of gelatin, chitosan, and polylysine.
The method of claim 1,
The polymer precursor 2 is a compound containing two or more acrylate structures represented by the following Chemical Formula 3, a method for producing a biodegradable organic-inorganic hybrid microcapsule.
[Chemical Formula 3]

(In Chemical Formula 3,
Each of R ₃ is independently and at the same time one or more acrylates or one or more heteroatoms or not, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or alkylene having 1 to 50 carbon atoms and carbon number It may contain 3 to 60 cyclic hydrocarbon groups)
The method of claim 5, wherein the compound containing two or more acrylate structures is ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tri(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, Poly(ethylene glycol) diacrylate, propylene glycol diacrylate, di(propylene glycol) diacrylate, tri(propylene glycol) diacrylate, tetra(propylene glycol) diacrylate, poly(propylene glycol) diacrylate , Butanediol diacrylate, hexanediol diacrylate, hexanediol ethoxylate diacrylate, neopentyl glycol propoxylate (1 PO/OH) diacrylate, trimethylolpropane ethoxylate (1 EO/OH) methyl Ether diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane propoxylate triacrylate, tris[2-(acryloyloxy)ethyl]isocyanu Rate, trimethylolpropane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, hydroxypivalyl hydroxypivalate bis[6-(acryloyloxy)hexanoate] At least one selected from the group consisting of, biodegradable organic-inorganic hybrid microcapsules manufacturing method.
The method of claim 1, wherein the inorganic particles contain 0.001 to 30% by weight based on the total weight of the first solution in the continuous phase.
The method of claim 1, wherein the polymer precursor 1 comprises 0.001 to 20% by weight based on the total weight of the second solution in the continuous phase.
The method of claim 1, wherein the polymer precursor 2 comprises 0.001 to 30% by weight based on the total weight of the dispersed solution.
The method of claim 1, wherein the dispersed phase solution is
Pentane, hexane cyclohexane, heptane, octane, isododecane, dodecane, ethyl ether, butyl ether, methyl-t-butyl ether, ethyl acetate, butyl acetate, ethyl butyrate, methyl ethyl ketone, benzene, toluene, xylene, Dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethicone, and a method for producing a biodegradable organic-inorganic hybrid microcapsule further comprising at least one solvent selected from the group consisting of cyclomethicone.
The method of claim 1,
The inorganic particles are in the group consisting of haloysite nanotubes, laponite, kaolinite clay, colloidal silica, calcium hydroxide, magnesium hydroxide, magnesium oxide, alumina, aluminum hydroxide, aluminum phosphate, calcium pyrrolate, aluminum pyrrolate, and zinc pyrrolate. At least one selected,
Method for producing biodegradable organic-inorganic hybrid microcapsules.
The method of claim 1,
The active ingredient is at least one selected from the group consisting of fragrances, dyes, catalysts, antioxidants, and drugs.
Method for producing biodegradable organic-inorganic hybrid microcapsules.
A capsule according to any one of claims 1 to 12,
It includes a dispersion phase positioned in the core and an outer wall of the hybrid capsule surrounding the outside of the dispersion phase, and includes a dispersion phase of 1 to 90% by weight based on the total weight of the capsule,
Characterized in that it has a strength of 50 to 200 MPa or less,
Biodegradable organic/inorganic hybrid microcapsules.
The method of claim 13, further comprising: a dispersed phase; And Biodegradable organic-inorganic hybrid microcapsules comprising an outer wall of a hybrid capsule including poly(β-amino ester) and inorganic particles formed at the interface of the dispersed phase.
The biodegradable organic-inorganic hybrid microcapsules according to claim 13, wherein the average particle diameter is 0.1 μm or more and 1000 μm or less.

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