KR20200004152A - Method for prreparing organic-inorganic hybrid microcapsule - Google Patents

Abstract

The present invention relates to a method for manufacturing a biodegradable organic-inorganic hybrid microcapsule which manufactures a continuous phase comprising an outer wall reinforcing material and an inorganic particle of a capsule, followed by forming a pickering emulsion by mixing with a reactive material or a dispersion phase containing the reactive material and an active component by using the same and by allowing the outer wall reinforcing material and the reactive material to proceed with polymerization at the interface, thereby being able to effectively express activity thereof by pressure after stably supporting the active component, and also being able to be slowly released at room temperature unlike an existing method.

Description

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

The present invention relates to a method for producing an organic-inorganic hybrid microcapsules, and more particularly, it is possible to effectively express the activity by pressure after supporting the active ingredient stably, as well as the characteristics that are slowly released at room temperature unlike conventional It relates to a method for producing a biodegradable organic-inorganic hybrid microcapsules that can be represented.

Encapsulation is known as a method to solve the problem that the active ingredient loses its intrinsic properties due to factors such as light, heat, etc. during storage, or the activity is low due to low concentration due to physical phenomenon such as evaporation. This encapsulation not only increases the stability of the active ingredient but also has the advantage of activating the active ingredient at a desired time by the user, and thus has been used in many industrial fields. Representative methods for activating the encapsulated active ingredient include a method of slowly releasing or sustaining the active ingredient by inducing breakage of the capsule outer wall by a factor such as pressure or inducing a small hole in the capsule outer wall.

Commercially used encapsulation materials are known as melamine-formaldehyde resin based capsules, but there is a problem that formaldehyde, which is a toxic substance, may exist in the manufacturing process of the microcapsules. For this reason, there is a growing interest in new capsules free of formaldehyde.

As a solution to this, liposome capsules, coacervation, microsponges, and the like have been proposed. However, these methods show limitations of reducing the stability of the capsule by the surfactant and the ionic component in the formulation, lowering the carrying capacity of the active ingredient, or controlling the release thereof, which is insufficient to replace the melamine capsule.

In another method, a capsule based on an inorganic material such as silica has been proposed as a new alternative. However, in the case of the capsule prepared by the above method, as the amphipathy of the core material increases, it is difficult to form the outer wall after the precursor organopolysiloxane moves to the interface. There is a problem with this wide application. In addition, the capsule has a disadvantage that it is difficult to control the degree of activation of the active ingredient due to the low elasticity and high hardness.

On the other hand, there are many industrially used organic polymer-based capsules, such as polyacrylic, polyurea-based, polyurethane-based, etc. The capsule is considered as an alternative to the advantage of not using formaldehyde in the polymerization process, wide versatility and excellent economy . However, the organic polymer-based capsule is difficult to express the active ingredient due to the high elasticity of the polymer itself, the breakability due to the pressure.

Therefore, there is a need for the development of biodegradable capsule materials that are less toxic and have high versatility, economical efficiency, and easily control the activity of active ingredients.

It is an object of the present invention to provide biodegradable organic-inorganic hybrid microcapsules that are low in toxic substances and have high versatility, and are excellent in economic efficiency, and in particular, the activity of active ingredients can be easily expressed and excellent in releasing slowly 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 prepared by the above method.

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

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

And a third step of forming a pickling emulsion by adding a dispersed phase solution to the first solution, and then forming a capsule outer wall by interfacial polymerization by adding a second solution.

The capsule outer wall comprises a poly (β-amino ester) and inorganic particles,

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

Provided is a method for preparing biodegradable organic-inorganic hybrid microcapsules.

According to another embodiment of the present invention, a capsule according to the method, comprising a dispersed phase located in the core and a hybrid capsule outer wall surrounding the outside of the dispersed phase, comprising 1 to 90% by weight of the dispersed phase relative to the total weight of the capsule. To provide a biodegradable organic-inorganic hybrid microcapsules.

In the present invention, there are few toxic substances and have high versatility, economical efficiency, the activity of the active ingredient can be easily expressed by adjusting the strength of the outer wall of capsules, and the internal dispersed phase is gradually released over time. There is an effect to provide a biodegradable organic-inorganic hybrid capsule.

In addition, the present invention has the effect of providing an environmentally friendly organic-inorganic hybrid capsule when using a natural polymer, its derivatives and a naturally-derived polymer as a precursor when producing the capsule.

1 briefly illustrates the contact angle of inorganic particles.
Figure 2 shows the principle of the method for producing a biodegradable organic-inorganic hybrid capsule of the present invention.
Figure 3 shows a comparison of the release behavior of the volatile oil over time of Comparative Examples 1 and 2 and Examples 1, 6 to 8.
Figure 4 shows the comparison of the laundry evaluation results of Comparative Examples 3 to 4 and Example 10.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, 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 embodies a particular 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.

Also, in general, the diameter of the microcapsules may range from 1 to 1,000 μm. In the context of the present invention, the term "microcapsules" also includes nanocapsules, ie capsules <1 μm in diameter. 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 for preparing biodegradable organic-inorganic hybrid microcapsules and microcapsules prepared by using the same will be described.

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

Preferably, the capsule outer wall may comprise an organic-inorganic hybrid structure comprising a poly (β-amino ester) and inorganic particles.

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

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

And a third step of forming a pickling emulsion by adding a dispersed phase solution to the first solution, and then forming a capsule outer wall by interfacial polymerization by adding a second solution.

The capsule outer wall comprises a poly (β-amino ester) and inorganic particles,

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

Provided are methods for preparing biodegradable organic-inorganic hybrid microcapsules.

In the present invention, after preparing the continuous phase including the outer wall reinforcing material and the inorganic particles to include the polymer and inorganic particles at the interface when preparing the capsule, by using the mixed or dispersed phase containing the reactive material and the reactive material and the active ingredient By forming a pickling emulsion and allowing the outer wall reinforcing material and the reactive material to be polymerized at an interface, the toxic material is characterized by providing an organic-inorganic hybrid microcapsules which show little versatility and economy.

In addition, the inorganic particles are contained in the capsule outer wall to adjust the hardness and elasticity of the outer wall, it is possible to manufacture a capsule that can easily express the activity of the active ingredient than conventional.

In addition, the present invention can produce an environmentally friendly organic-inorganic hybrid capsule when using a natural polymer, its derivatives and a naturally-derived polymer as a precursor.

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

The first step is to prepare a continuous phase first to form a pickling emulsion, which will be described later.

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

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

Preferably, the first solution of the continuous phase may include inorganic particles as a precursor of the capsule outer wall material, and the second solution of the continuous phase may include a polymer precursor for strengthening the outer wall.

The inorganic particles serve as pickling particles to enhance the stability of the dispersed phase in the interfacial polymerization in the future, and is also mixed during the polymer polymerization process to increase the hardness of the capsule outer wall and lower the elasticity.

The inorganic particles may comprise 0.001 to 30% by weight based on the total weight of the first solution of 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, and more preferably based on 100 parts by weight of the dispersed phase solution based on the total weight of the dispersed phase solution. 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% by weight or less based on the first solution), there is a problem that a pickling emulsion cannot be formed, and when 100 parts by weight or more (30% by weight or more based on the first solution) is formed, a gel is formed. 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, more preferably 2 nm or more and 500 nm or less.

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

On the other hand, the first step may further comprise a surface treatment step of the inorganic particles.

The contact angle θ used to define the properties of the inorganic particles may be defined as shown in FIG. 1. As shown in FIG. 1, after the tangent line is drawn at the point where the 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 called a contact angle.

The inorganic particles are substances having a contact angle of 90 degrees or less when present in the continuous phase and the dispersed phase. For such inorganic particles, the inorganic particles may be controlled to act as pickling particles through surface treatment.

Therefore, the first step may further include a surface treatment step for 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 or less, preferably 5 degrees or more and 90 or less, more preferably 10 degrees or more and 90 degrees or less.

The surface treatment step may include the step of adding a surface treatment material for adjusting the contact angle of the inorganic particles to the first solution of the continuous phase containing the inorganic particles.

The surface treatment material may be 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, alkoxysilanes and derivatives thereof are included, and one or more selected from the above materials may be used.

In addition, the first solution of the continuous phase may include distilled water as a residual amount of solvent in addition to the inorganic particles. The distilled water can be used by purification according to methods well known in the art.

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

The polymer precursor 1 may include 0.001 to 20% by weight based on the total weight of the second solution of the continuous phase. The outer wall reinforcing polymer precursor 1 may be 0.002 to 30 parts by weight, preferably 0.006 to 25 parts by weight, and more preferably 0.011 to 20 parts by weight based on 100 parts by weight of the dispersed phase solution based on the total weight of the dispersed phase solution. have. If the content of the polymer precursor 1 is 0.002 parts by weight or less (0.001% by weight or less based on the second solution), there is a problem in that the capsule is not formed, and when it is 30 parts by weight or more ((20% by weight or more based on the second solution), the reaction is not uniform. There is a problem that the stability of the capsule falls.

The polymer precursor 1 for strengthening 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 use at least one 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.

As a preferred example, the compound having two or more amine groups may include a compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

Each R ₁ is independently, at the same time with or without at least one amine 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 carbon atoms May comprise 3 to 60 cyclic hydrocarbon groups,

n is an integer from 1 to 5000)

In the present invention, the cyclic hydrocarbon having 3 to 30 carbon atoms may each independently include a cyclic saturated or unsaturated hydrocarbon (aromatic hydrocarbon), with or without at least one amine group or at least one hetero atom.

More specifically, the compound having two or more amine groups is methylenediamine (methylenediamine), ethylenediamine (ethylenediamine), diethylenetriamine (diethylenetriamine), triethylenetetramine (triethylenetetramine), tetraethylenepentaamine (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, 2,5-Diaminotoluene, 3,3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane (3,4'- Diaminodiphenylmethane), 4,4'-Diaminodiphenylmethane, 4,4'-ethylenedianiline, 4,4'-diaminodiphenyl sulfide (4,4'-Diaminodiphenylmethane) 4,4'-Diaminodiphenyl sulfide), 4,4'-oxydianiline (4,4'-Oxydianiline), pararosaniline base (Pararosaniline Base), melamine and tetrakis (4-aminophenyl) methane ( Tetrakis (4-aminophenyl) methane) may be used one or more selected from the group consisting of.

Compound having two or more hydroxy groups may include a compound represented by the following formula (2).

[Formula 2]

(In Formula 2,

R ₂ is each independently or simultaneously having at least one hydroxy group or at least one hetero atom, having 1 to 50 alkylenes, having 3 to 60 cyclic hydrocarbon groups, or having 1 to 50 alkylenes and 3 to 3 carbon atoms. May comprise from 60 to 60 cyclic hydrocarbon groups,

n is an integer from 1 to 5000)

More specifically, the compound having two or more hydroxyl groups is methanediol, ethylene glycol (Ethyelene glycol), propanediol (Propanediol), butanediol (Butanediol), pentanediol (Pentanediol), hexanediol (Hexanediol) Heptanediol, Octanediol, Nonanediol, Nonanediol, Decanediol, Dodecanediol, Tedecanediol, Tetradecanediol, Hexadecanediol, Hexadecanedithy, Ethylene glycol ), Thritol, Ribitol, Galitolitol, Galactitol, Fuctitol, Iditol, Inositol, Volemitol, Maltotriitol Maltotetriitol (Maltotetraitol), Polyglycitol (Polyglycitol), Arabbitol (Arabitol), Erythritol, Glycerol, Isomalt, Lactitol, Maltitol, Maltitol, Mannitol (Mannitol) Sorbitol, Xylitol, Sucrose , Polyethylene glycol, polypropylene glycol, polyvinyl alcohol, VP / vinyl alcohol copolymer, butenediol / vinyl alcohol copolymer Copolymer, Polyglycerin, Glyceryl Polyacrylate, Dimethiconol, Bis-Hydroxyethoxypropyl Dimethicone, Bis-hydroxypropyl Dimethicone Bis-Hydroxypropyl Dimethicone), hydroxypropyldimethicone (Hydroxypropyldimethicone) and bis-hydroxyethyl tromethamine (Bis-Hydroxyethyl Tromethamine) may be used at least one selected from the group consisting of.

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

In addition, the second solution of the continuous phase may include distilled water as a residual amount of solvent in addition to the polymer precursor 1. The distilled water can be used by purification according to methods well known in the art.

On the other hand, the second step is to prepare a dispersed phase for mixing with the continuous phase.

The dispersed phase includes a specific reactive material or a reactive component and an active ingredient which are precursors of the capsule outer wall material generated in a future encapsulation process. The dispersed phase refers to a substance that is kept 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 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 linear or nonlinear hydrocarbon-based solvent such as pentane, hexane cyclohexane, heptane, octane, isododecane, dodecane, ethers such as ethyl ether, butyl ether, methyl-t-butyl ether, etc. Derivative derivative solvent containing group, derivative derivative solvent containing ester group such as ethyl acetate, butyl acetate, ethyl butyrate, ketone solvent such as methyl ethyl ketone, aromatic solvent such as benzene, toluene, xylene, dichloromethane, Haloalkane-based solvents such as dichloroethane, chloroform and carbon tetrachloride, and silicone-based solvents such as dimethicone and cyclomethicone, and the like, and these may be selected and used.

In addition, the solvent applicable to the above-mentioned disperse phase is applicable to a continuous phase as needed.

The solvent content in the dispersed phase solution may be included as a residual amount, it can be used by appropriately adjusted according to the additive component.

Reactive materials that are precursors of the capsule outer wall material included in the dispersed phase are included. The reactive material is a material capable of forming the outer wall of the capsule by reacting with the outer wall reinforcing material dissolved in the continuous phase, and is a material that melts well in the dispersed phase.

Such reactive materials are referred to herein as polymeric precursors 2. The polymer precursor 2 includes precursors of polymer materials capable of interfacially reacting with the polymer precursor 1 for external wall reinforcement to form a poly (β-amino ester).

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

[Formula 3]

(In Chemical Formula 3,

Each R ₃ independently or simultaneously has one or more acrylates or one or more heteroatoms, an alkylene having 1 to 50 carbon atoms, a cyclic hydrocarbon group having 3 to 60 carbon atoms, or an alkylene and carbon number having 1 to 50 carbon atoms; May contain 3 to 60 cyclic hydrocarbon groups)

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

The polymer precursor 2 may include 0.001 to 30% by weight, preferably 0.005 to 25% by weight, 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 less than 0.001% by weight, there is a problem in that the capsule is not formed, and in the case of 30% by weight or more, there is a problem in that the stability of the capsule is reduced due to a heterogeneous reaction.

The active ingredient is a substance whose activity is desired to be maintained by the resulting capsule, and is the substance whose activity is expressed as the outer wall is later destroyed. The active ingredient may be substituted for the disperse phase which is a solvent when the liquid at room temperature, otherwise it may vary depending on solubility. Examples of the active ingredient may include flavors, dyes, catalysts, antioxidants, drugs, and the like, and may be used to select one or more kinds.

Even if the active ingredient is included in a small amount, its properties may be expressed, and since the active ingredient may itself be a dispersed phase, it may be included up to 100 parts by weight based on 100 parts by weight of the dispersed phase solution as necessary. Thus, the content of the active ingredient is not greatly limited, and the content can be set according to the ingredient material used, and can be used as 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 the poly (β-amino ester) which is a biodegradable polymer in order to increase the capsule stability It may further include.

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

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

[Formula 4]

(In Formula 4,

Each R ₄ independently of one or more acid chlorides (-COCl) or one or more heteroatoms at the same time, alkylene having 1 to 50 carbon atoms, cyclic hydrocarbon group having 3 to 60 carbon atoms, or having 1 to 50 carbon atoms Alkylene and a cyclic hydrocarbon group having 3 to 60 carbon atoms)

The compound including two or more isocyanate structures may be a compound represented by the following Formula 5.

[Formula 5]

(In Chemical Formula 5,

Each R ₅ is independently independently having at least one isocyanate or at least one hetero atom at the same time, 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 having 3 carbon atoms. To 60 cyclic hydrocarbon groups)

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

[Formula 6]

(In Chemical Formula 6,

Each R ₆ independently of each other has one or more chloroformates (-OCOCl) or one or more heteroatoms, alkylene of 1 to 50 carbon atoms, a cyclic hydrocarbon group of 3 to 60 carbon atoms, or 1 to 50 carbon atoms Alkylene and a cyclic hydrocarbon group having 3 to 60 carbon atoms)

More specifically, the compound having two or more acid chlorides may be malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, pimeloyl chloride. At least one selected from the group consisting of (Pimeloyl chloride), suberoyl chloride, sebacoyl chloride, azelaic acid dichloride, and dodecanedioyl dichloride This can be used.

More specifically, the compound having two or more isocyanates includes methylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate (Tolylene-2). , 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-die Phenylphenyl isocyanate) (4,4'-Methylenebis (2,6-diethylphenyl isocyanate)), isoprene 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) ), Diisocyanatobutane, Hexamethylene diisocyanate, Diisocyanatooctane, Diisocyanatododecane and 1,6-diisocyanato-2,2 At least one selected from the group consisting of, 4-trimethylhexane (1,6-Diisocyanato-2,2,4-trimethylhexane) may be used.

More specifically, the compound having two or more chloroformates includes ethylene bis (chloroformate), diglycolyl chloride, oxydiethylene bis (chlorodimate) 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)) One or more selected from the group consisting of can be used.

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

Specifically, the microcapsules of the present invention, as shown in FIG. 2, form a pickling emulsion after mixing of a continuous phase and a dispersed phase solution, and are formed through interfacial polymerization. At the interface, there are polymer and inorganic particles, which are capsule outer wall materials.

More preferably, the first solution of the continuous phase and the dispersed phase solution may be mixed to form a pickling emulsion, and then the second solution of the continuous phase may be added thereto and the interfacial polymerization may be performed to form microcapsules.

In the third step, when the pickling emulsion is formed by mixing the first solution and the dispersed phase solution of the continuous phase, 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 or less at room temperature. It may be below RPM.

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

If necessary, the method of the present invention may further comprise the step of adding 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 one preferred embodiment, the method of the present invention may further comprise the step of adding a dispersion stabilizer in the first or third step.

The dispersion stabilizer may be used for the purpose of increasing the dispersibility of the capsule produced after the reaction. The dispersion stabilizers include 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 their quaternized forms; 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 Ethers), poly (vinylether-co-maleic anhydride) and the like, as well as poly (ethyleneimine), poly ((meth) acrylamide), poly (alkylene oxide-co-dimethylsiloxane), poly (aminodimethyl Siloxane) and the like can be used.

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

After the polymerization of the third step, if necessary, further comprising the step of concentrating or drying the solution containing the microcapsules, the conditions are not limited.

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 dispersed phase located in the core and a hybrid capsule outer wall surrounding the outside of the dispersed phase, the dispersed phase of 1 to 90% by weight relative to the total weight of the capsule Including an organic-inorganic hybrid microcapsules may be provided.

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

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

Herein, 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 optionally formed using a catalyst. In this case, a catalyst may be included on the outer wall of the final capsule structure.

In addition, the inorganic particles are included in the interfacial polymerization process to adjust the hardness and elasticity of the outer wall of the capsule to improve the breakability.

In addition, the biodegradable organic-inorganic hybrid microcapsules may include 1 to 90% by weight of the dispersed phase 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 organic-inorganic hybrid capsule outer wall which is polymerized and included at the interface of the microcapsules can control the strength of the organic-inorganic hybrid capsule, and thus can easily express the activity of the active ingredient. In particular, the organic-inorganic hybrid capsule of the present invention exhibits a suitable strength range for the product application, for example, may exhibit a strength of about 50 to 200 MPa or about 50 to 160 MPa, it is easy to control the strength within the range when applying the product 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 operation and effect of the invention will be described in more detail with reference to specific examples. However, this is presented as an example of the invention, whereby the scope of the invention is not limited in any sense.

<Example>

In the present invention, 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). The strength was calculated by dividing the maximum load by the contact area.

(2) size

Capsule size was measured using a Malvern Mastersizer 3000.

Experimental Example 1 Comparison of Capsule Strength with Various Inorganic Particle Materials

In order to prescribe and use the microcapsules in the product, proper strength is required, but if the strength of the microcapsules is too high, it is difficult to apply to the product, so it is important to adjust the strength. Therefore, strength comparison experiments were conducted on conventional organic microcapsules and 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 the strength and size of each capsule were measured. The measurement results are shown in Table 1.

Comparative Example 1

First stage

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).

2nd step

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

3rd step

-amino ester) 마이크로 캡슐을 제조하였다.At 2000 RPM, the emulsion was prepared by slowly adding the dispersed phase solution to the continuous phase 1 (first solution). Thereafter, the speed of the stirrer was lowered to 1000 RPM, and the continuous phase 2 (second solution) was added to the emulsion, followed by interfacial polymerization at 80 ° C. for 12 hours.

-amino ester) microcapsules were prepared.

Examples 1-5

First stage

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). Also, 1 g of polyethyleneimine was added to 9 g of distilled water to prepare a continuous phase 2 (second solution).

2nd step

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

3rd step

At 2000 RPM, the continuous phase 1 (first solution) was slowly added while stirring the dispersed phase solution to form a pickling emulsion. Thereafter, the speed of the stirrer was lowered to 1000 RPM, and then the continuous phase 2 (second solution) was added to the pickling emulsion, followed by interfacial polymerization at 80 ° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsules.

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

In the results of Table 1, the organic microcapsules of Comparative Example 1 was too high strength, such as 443.1 MPa, it was difficult to apply to the product, it was also difficult to control the strength showed a problem.

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 to a strength suitable for use in a product about 56.3 to 80.9 MPa. In addition, Examples 1 to 5 also showed the advantage of easy to adjust the strength to improve the workability and usability.

Experimental Example 2 Capsule Strength Adjustment

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

Examples 6-9

First stage

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 shown in Table 3 to prepare a continuous phase 2 (second solution).

2nd step

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

3rd step

At 2000 RPM, the continuous phase 1 (first solution) was slowly added while stirring the dispersed phase solution to form a pickling emulsion. Thereafter, the speed of the stirrer was lowered to 1000 RPM, and then the continuous phase 2 (second solution) was added to the pickling emulsion, followed by interfacial polymerization at 80 ° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsules.

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

In the results of Table 2, the present invention was able to control the strength of the capsule according to the polymer content, in the case of Examples 11 and 12 as the polyisocyanate and polyethyleneimine content increases compared to Example 1, the strength of the capsule becomes stronger It was confirmed.

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

Experimental Example 3 Release Behavior of Volatile Oils

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, in Comparative Example 1, Comparative Example 2, Example 1, Examples 7 to 9, the release behavior of the volatile oil in the dispersed phase was compared.

The release behavior of volatile oil was measured for 4 hours at 120 ° C., and measured using MA-100 manufactured by Satorius. The results are shown in Table 4 and FIG. 3.

Comparative Example 2

First stage

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

2nd step

3 g of TEOS was added to 30 g of dodecane to prepare a dispersed phase.

3rd step

At 2000 RPM, the pickling emulsion was prepared by slowly stirring the dispersed phase into the continuous phase. Thereafter, the pH of the emulsion was adjusted to 10 using NaOH, followed by an interfacial polymerization reaction 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
Remaining amount (%) 33.5 4.3 4.6 8.8 16.3 21.5 26.4

From the results of Table 4 and Figure 3, Examples 9 to 12 confirmed that the internal dispersed phase is gradually released over time. In addition, as in Examples 11 and 12, the higher the content of polyisocyanate and polyethyleneimine, the lower the amount released, but overall exhibiting excellent sustained release oil release.

Experimental Example 4 Preparation of Flavor Capsules and Laundry Evaluation

As a practical application, after preparing the flavor capsules of Comparative Examples 3 to 4 and Example 10 as described below, the strength and size were measured, and laundry evaluation was also performed.

That is, the biodegradable organic-inorganic hybrid capsules of the present invention was expected to exhibit high odor due to the expression and breaking properties of the excellent active ingredient, in order to verify this, Comparative Example 2 and Example 1 was prepared, the strength Was measured and the laundry was evaluated.

The fragrance oil used commercially available oil. Then, known polyurea, polyamide, polyurethane, polyester, melamine-formaldehyde resin capsules were set as Comparative Examples 3 to 4.

1) Strength and size: Measured according to the method described above.

2) laundry evaluation

For the test fiber, a commercially available cotton towel (30 × 20 cm) was prepared, and a general laundry detergent was used in a standard use, and washed repeatedly with a washing machine five times, followed by dehydration. Each microcapsules of Comparative Examples and Examples were prepared in 1% aqueous solution, and then quantitatively added to a standard washing machine (0.67 ml / 1 l wash water) in a stirred washing machine, treated with a rinse course, and cotton towels were taken out after dehydration. . The cotton towels were dried at a humidity of 30% and a temperature of 25 ° C. for 12 hours.

At this time, three time points were set (immediately after washing, after drying, and after rubbing), and 20 experienced panelists evaluated sensory strength by performing sensory evaluation. The fragrance intensity was given from the lowest zero to the highest five points based on the zero point of the non-treated cotton towel, and repeated three or more times to evaluate the reverberation with the average value. The results are shown in Table 5 and FIG.

Comparative Example 3

First stage

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

2nd step

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

3rd step

-amino ester) 마이크로 캡슐을 제조하였다.At 2000 RPM, the emulsion was prepared by slowly stirring the dispersed phase into the continuous phase 1 (first solution). Thereafter, the speed of the stirrer was lowered to 1000 RPM, and the continuous phase 2 (second solution) was added to the emulsion, followed by interfacial polymerization at 80 ° C. for 12 hours.

-amino ester) microcapsules were prepared.

Comparative Example 4

First stage

Sodium dodecyl sulfate, Tween 20, Arabic gum, pre-melamine formaldehyde solution (Pre-melamine formaldehyde solution) was dispersed in distilled water 54g to prepare a continuous phase.

2nd step

At 2000 RPM conditions, an emulsion was made by slowly adding 30 g of perfume (dispersed phase) to the continuous phase.

3rd step

After the speed of the stirrer was lowered to 1000 RPM, the pH was lowered to 5 with citric acid and then capsule production was performed at 70 ° C. for 3 hours. After terminating the reaction using Tromethamine to pH 7.5, the melamine-formaldehyde resin capsules were prepared.

Example 10

First stage

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

2nd step

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

3rd step

At 2000 RPM, the continuous phase 1 (first solution) was slowly added while stirring the dispersed phase to form a pickling emulsion. Thereafter, the speed of the stirrer was lowered to 1000 RPM, and then the continuous phase 2 (second solution) was added to the pickling emulsion, followed by interfacial polymerization at 80 ° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsules.

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 friction 1.91 2.34 4.47

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

Experimental Example 5 Evaluation of Biodegradation of Flavor Capsules

In this Experimental Example, Example 11 was prepared by the following method, and the outer wall material of the fragrance capsule of the present invention was separated to evaluate and compare 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

First stage

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

2nd step

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

3rd step

At 2000 RPM, the continuous phase 1 was slowly added with stirring to form a pickling emulsion. Thereafter, the speed of the stirrer was lowered to 1000 RPM, the continuous phase 2 was added to the pickling emulsion, and the interpolymerization reaction was performed at 80 ° C. for 12 hours to prepare a biodegradable organic-inorganic hybrid microcapsules.

Separation of capsule outer wall material

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

Biodegradation Measurement

The biodegradability was measured according to the following calculation method after measuring the chemical oxygen demand (COD) and the biochemical oxygen demand (BOD) according to the well-known OECD 301 F method.

COD measurements were measured according to the ISO 6060 method. Briefly, the COD was calculated from the molar number of dichromic acid used in the oxidation reaction after titrating the appropriate amount of the sample with sulfuric acid and excess potassium dichromate and titrating the remaining potassium dichromate using FAS (Ferrous ammonium sulfate).

For BOD measurement, an aqueous solution containing microorganisms was prepared according to the method specified in OECD 301, an appropriate amount of sample (0.1 g or more per L) was added, and oxygen consumption was measured by a respirometer for 28 days. At this time, potassium hydroxide (Potassium hydroxide) solution was used to remove the carbon dioxide generated by the microorganism, and the blank solution containing no sample was measured at the same time to calculate the BOD through the following Equation 1.

[Equation 1]

Biodegradability was obtained using the following equation.

[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 an excellent degree of biodegradation compared to Comparative Example 3, Example 11 using natural polymers confirmed a better degree of biodegradation.

Claims (15)

A first step of preparing a continuous solution including the inorganic particles and the second solution including the polymer precursor 1 for strengthening the outer wall;
A second step of preparing a biodegradable polymer precursor 2 reacting with the outer wall reinforcing polymer precursor 1 or an active ingredient and a dispersed phase solution including the polymer precursor 2; And
And a third step of forming a pickling emulsion by adding a dispersed phase solution to the first solution, and then forming a capsule outer wall by interfacial polymerization by adding a second solution.
The capsule outer wall comprises a poly (β-amino ester) and inorganic particles,
The outer wall reinforcing polymer precursor 1 and the biodegradable polymer precursor 2 each independently comprises one or more precursors for forming a poly (β-amino ester),
Method for preparing 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 Chemical Formula 1, a compound having two or more hydroxyl groups represented by the following Chemical Formula 2, and a natural polymer,
Method for preparing biodegradable organic-inorganic hybrid microcapsules.
[Formula 1]

(In Formula 1,
Each R ₁ is independently independently having at least one amine 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 carbon atoms May comprise 3 to 60 cyclic hydrocarbon groups,
n is an integer from 1 to 5000)
[Formula 2]

(In Formula 2,
Each R ₂ independently or simultaneously has one or more hydroxy groups or one or more heteroatoms, 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 having 3 carbon atoms May comprise from 60 to 60 cyclic hydrocarbon groups,
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, and 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, pararosanilin base, melamine and tetrakis (4-aminophenyl Biodegradable organic-inorganic hybrid microcapsules selected from the group consisting of methane Manufacturing method.
The method of claim 1, 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 formula (3), a method for producing a biodegradable organic-inorganic hybrid microcapsules.
[Formula 3]

(In Chemical Formula 3,
Each R ₃ independently or simultaneously has one or more acrylates or one or more heteroatoms, an alkylene having 1 to 50 carbon atoms, a cyclic hydrocarbon group having 3 to 60 carbon atoms, or an alkylene and carbon number having 1 to 50 carbon atoms; May contain 3 to 60 cyclic hydrocarbon groups)
According to claim 1, wherein the compound having two or more acrylate groups are 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, neopentylglycol diacrylate, pentaerythritol triacrylate, trimethylolpropane Triacrylate, trimethylolpropane propoxylate triacrylate, tris [2- (acryloyloxy) ethyl] isocyanurate, trimethylolpropane ethoxylate triacrylate, di (trimethylolpropane) tetraacrylate , Pentaerythritol tetraacrylate, hydroxy pivalyl hydroxy pivalate 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 comprise 0.001 to 30% by weight based on the total weight of the first solution of 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 of 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 phase solution.
The method of claim 1, wherein the dispersed phase solution
Pentane, hexane cyclohexane, heptane, octane, isododecane, dodecane, ethyl ether, butyl ether, methyl-t-butyl ether, ethyl acetate, butyl acetate, ethyl butyrate, methylethylketone, benzene, toluene, xylene, Dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethicone and cyclomethicone further comprises at least one solvent selected from the group consisting of biodegradable organic-inorganic hybrid microcapsules.
The method of claim 1,
The inorganic particles are in the group consisting of halosite nanotubes, laponite, kaolinite clay, colloidal silica, calcium hydroxide, magnesium hydroxide, magnesium oxide, alumina, aluminum hydroxide, aluminum phosphate, calcium pyrolate, aluminum pyrrolate and zinc pyrolate One or more selected
Method for preparing biodegradable organic-inorganic hybrid microcapsules.
The method of claim 1,
The active ingredient is one or more selected from the group consisting of perfumes, dyes, catalysts, antioxidants and drugs
Method for preparing biodegradable organic-inorganic hybrid microcapsules.
A capsule according to any one of claims 1 to 12,
A dispersed phase located in the core and a hybrid capsule outer wall surrounding the outside of the dispersed phase, comprising from 1 to 90% by weight of the dispersed phase relative to the total weight of the capsule,
Biodegradable organic-inorganic hybrid microcapsules.
14. The method of claim 13, further comprising: a dispersed phase; And a hybrid capsule outer wall including poly (β-amino ester) and inorganic particles formed at an interface of the dispersed phase.
The biodegradable organic-inorganic hybrid microcapsule according to claim 13, wherein the average particle diameter is 0.1 μm or more and 1000 μm or less.

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