JP2021528239A - Method for producing redispersible polyurea microcapsules and redispersible polyurea microcapsules - Google Patents

Abstract

A step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a step of combining the first mixture with a second mixture. A step of mixing to prepare a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, a step of filtering the cured third mixture, and a filtered first step. Polyurea microcapsules produced by a method comprising the step of drying a mixture of three.

Description

The embodiments of the present disclosure relate to redispersible polyurea microcapsules and methods for producing redispersible polyurea microcapsules.

Encapsulation of a functional active material is an attractive way of storing the active material as well as protecting it from the surroundings until it is required to perform its proper use. The microencapsulated material can be used for sustained release drugs, electrorheological fluids, expandable flame retardant powders, flavor preservation, electrophoretic display applications, textiles, biotechnology and inorganic metal salt catalysts.

The present invention provides polyurea microcapsules with high encapsulation efficiency.

The following summary provides a simplified summary to provide a basic understanding of some aspects of the disclosure discussed herein. This overview is not an extensive overview of the disclosure discussed herein. It is not intended to identify important factors or to clarify the scope of such disclosure. Its sole purpose is to present some concepts in a simplified form as a prelude to a more detailed explanation presented later.

According to one aspect of the present disclosure, a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and the above. A step of mixing the first mixture with the second mixture to prepare a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and curing. Polyurea microcapsules produced by a method comprising a step of filtering the third mixture and a step of drying the filtered third mixture are provided.

According to one aspect of the present disclosure, a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a second. A step of mixing the mixture of 1 with a second mixture to make a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and a cured third mixture. A step of filtering, a step of drying the filtered third mixture, and a step of mixing the dried third mixture with water and starch to prepare a mosquito repellent material (mosquito knockdown material and / or mosquito repellent). A process and a method including the process are provided.

According to one aspect of the present disclosure, which is a method of knocking down or repelling mosquitoes, a step of applying a mosquito-preventing material (mosquito knockdown material and / or a mosquito repellent) to a cloth, and the skin to be protected by the cloth. A step of covering, and a method including.
The mosquito repellent material (mosquito knockdown material and / or mosquito repellent) is a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, and a second step of adding an active ingredient and an isocyanate compound to a solvent. A step of making a mixture, a step of mixing a first mixture with a second mixture to make a third mixture, a step of emulsifying a third mixture, and a step of curing an emulsified third mixture. And a step of filtering the cured third mixture, a step of drying the filtered third mixture, and a mosquito repellent material (mosquito knockdown material and /) by mixing the dried third mixture with water and starch. Alternatively, it is produced by a method including a step of producing a mosquito repellent).

According to one aspect of the present disclosure, a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a second. A step of mixing the mixture of 1 with a second mixture to make a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and a cured third mixture. A consumer product comprising polyurea microcapsules produced by a method comprising a step of filtering the filter and a step of drying the filtered third mixture is provided. Examples of consumer products include detergents, fabric softeners, laundry glues, shampoos, hair conditioners, body washes, hygiene products, paints, coatings, and combinations thereof.

According to one aspect of the present disclosure, a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a second. A step of mixing the mixture of 1 with a second mixture to make a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and a cured third mixture. An antifungal product containing polyurea microcapsules produced by a method comprising a step of filtering the filter and a step of drying the filtered third mixture is provided. Examples of antifungal products include detergents, fabric softeners, starches, shampoos, hair conditioners, body washes, hygiene products, paints, coatings, and combinations thereof.

According to one aspect of the present disclosure, a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a second. A step of mixing the mixture of 1 with a second mixture to make a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and a cured third mixture. A mosquito repellent material (mosquito knockdown material and / or mosquito repellent) containing polyurea microcapsules produced by a method comprising filtering the filtered third mixture and drying the filtered third mixture is provided. .. Examples of mosquito repellent materials (mosquito knockdown materials and / or mosquito repellents) include detergents, fabric softeners, laundry glues, shampoos, hair conditioners, body wash, other hygiene products, paints, coating agents and the like. ..

According to the present invention, polyurea microcapsules having high encapsulation efficiency can be provided.

FIG. 1 is a flowchart showing an embodiment of the method for producing polyurea microcapsules of the present disclosure. FIG. 2 is a flowchart showing an embodiment of the method for producing polyurea microcapsules of the present disclosure. FIG. 3 shows photographs showing redispersed polyurea microcapsules produced by the method of the present disclosure and comparative polyurea microcapsules produced by the method example shown in FIG. 19 using guanidine carbonate as a cross-linking agent. include. FIG. 4 includes photographs showing the redispersed polyurea microcapsules produced by the method of the present disclosure and the redispersed comparative polyurea microcapsules produced by the method example shown in FIG. FIG. 5 includes photographs showing the time-dependent dispersion of redispersed polyurea microcapsules produced by the methods of the present disclosure with or without the addition of xanthan gum or gum arabic. FIG. 6 is a fluorescence optical microscope (FOM) image of polyurea microcapsules produced by the method of the present disclosure. FIG. 7 is an OM image of polyurea microcapsules produced by the method of the present disclosure. FIG. 8 is an SEM image of polyurea microcapsules produced by the method of the present disclosure at a magnification of 1,000 times. FIG. 9 is an SEM image of polyurea microcapsules produced by the method of the present disclosure at a magnification of 20,000 times. FIG. 10 includes an OM image of polyurea microcapsules produced by the methods of the present disclosure dispersed in a paint. FIG. 11 includes photographs showing polyurea microcapsules produced by the methods of the present disclosure, dispersed in different fabric softeners and exposed to ultraviolet (UV) light over time. FIG. 12 shows polyurea microcapsules made by the method of the present disclosure which are dispersed in water with starch, and polyurea microcapsules made by the method of the present disclosure which are dispersed in water with starch and gum. Includes photos. FIG. 13 is a photograph showing polyurea microcapsules prepared by the method of the present disclosure dispersed in polyvinyl alcohol (PVA), PVA, and polyurea microcapsules prepared by the method of the present disclosure dispersed in PVA and gum. including. FIG. 14 shows a fabric coated with CITREPEL® wrapped in polyurea microcapsules produced by the method of the present disclosure and not coated with polyurea microcapsules dispersed in a starch solution (left). It is a photograph showing the cloth (right). FIG. 15 is a photograph of a repellent test performed using the fabric shown in FIG. FIG. 16 shows a knockdown test using a filter paper coated with etofenprox and a filter paper not coated with polyurea microcapsules, which are dispersed in a starch solution and wrapped in polyurea microcapsules produced by the method of the present disclosure. Includes a graph showing the results. FIG. 17 is a flowchart showing an embodiment of the method for producing a mosquito repellent according to the present disclosure. FIG. 18 is a flowchart showing an embodiment of the mosquito repellent method in the present disclosure. FIG. 19 is a flowchart showing an example of a method for producing polyurea microcapsules.

The embodiments of the present disclosure relate to redispersible polyurea microcapsules and methods for producing redispersible polyurea microcapsules. Encapsulation of a functionally active material is an attractive way to not only protect the active material from its surroundings, but also to store it until it is required to perform its proper purpose. The redispersed polyurea microcapsules produced by the methods of the present disclosure exhibit high encapsulation efficiency with a wide range of active ingredients as compared to microcapsules produced by conventional methods. Redispersion of polyurea microcapsules produced by the methods of the present disclosure in water can be achieved without additives due to the high hydrophilicity of the polyurea microcapsules.

The present disclosure will now be described with reference to the drawings, but throughout, the same reference numbers are used to refer to the same elements. The various drawings are not necessarily drawn to scale from one drawing to another or within a given drawing, in particular the size of the components is arbitrary to facilitate comprehension of the drawing. Please understand that it is depicted in. The following description provides many specific details for illustration purposes in order to provide a complete understanding of the present disclosure. However, it is clear that this disclosure is feasible without these specific details. Further, embodiments different from the present disclosure are possible, and the present disclosure may be practiced and implemented in ways other than those described. The terms and expressions used in describing this disclosure are used to facilitate understanding of the disclosure and should not be construed as limiting this disclosure.

FIG. 19 is a flowchart showing an example of a method for producing polyurea microcapsules. Specific methods for producing such microcapsules include US Patent Application Publication Nos. 2013/0330292, 2013/0230574, 2013/0295149, 2011/0077188, 2006/0115604, 2002/0064656. No., 2002/0079599, US Pat. No. 5,635,211 which is incorporated herein by reference. FIG. 1 is a flowchart showing a method for producing polyurea microcapsules of the present disclosure. FIG. 2 is a flowchart showing in detail two embodiments of the method for producing polyurea microcapsules of the present disclosure. The methods of the present disclosure include a step of mixing a surfactant and a cross-linking agent to prepare a first mixture, a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture, and a first mixture. To make a third mixture, to emulsify the third mixture, to cure the emulsified third mixture, and to filter the cured third mixture. It comprises a step and a step of drying the filtered third mixture. In one embodiment, the method of the present disclosure further comprises the step of mixing the dried third mixture with a starch solution to make a mosquito repellent.

In the present disclosure, the cross-linking agent is mixed with the surfactant prior to emulsification of the mixture and added to the mixture of solvent, active ingredient and isocyanate, as shown in FIGS. 1 and 2. Emulsification can be carried out by homogenizing a mixture of cross-linking agent, surfactant, active ingredient and isocyanate at a specific rate. In contrast to the production methods of the present disclosure, in the example method shown in FIG. 19, a mixture of active ingredient and isocyanate is emulsified and then a cross-linking agent is added to the mixture. By adding a cross-linking agent prior to emulsifying the mixture, the polyurea microcapsules of the present disclosure have excellent dispersibility, excellent regenerative potential, good stability in dry and suspension forms, and additives. Alternatively, it can have high encapsulation efficiency without a catalyst.

1) Excellent dispersibility: Knockdown tests using microcapsules produced by the method of the present disclosure were carried out three times, and the results showed no variation, demonstrating excellent dispersibility. The results showing good and uniform performance show the good dispersibility of the microcapsules produced by the methods of the present disclosure. The superior dispersibility of the polyurea microcapsules produced by the method of the present disclosure as compared with the dispersibility of the microcapsules produced by the method example shown in FIG. 19 is also shown in FIG.

2) Regenerative ability: In the method example shown in FIG. 19, the possibility of agglutination or phase separation was observed several times, while in the method of the present disclosure, there was no agglutination or phase separation. The microcapsules produced by the method of the present disclosure showed good regenerative ability.

3) Stability in the dry state: No change in the redispersibility of the dry powder produced by the method of the present disclosure is observed over time (several months). Most capsules are in good condition and the only change is the loss of active ingredient released over time.

4) Stability in suspension: For microcapsules (without thickener) redispersed after the microcapsules settle, the microcapsules produced according to the present disclosure should be shaken as shown in FIG. Is more easily redistributed.

5) High encapsulation efficiency: No catalyst or additive is used in the methods of the present disclosure. The microcapsules produced by the methods of the present disclosure have high encapsulation efficiency, which is reported in the HPLC results in Table 1.

The method for producing polyurea microcapsules of the present disclosure is applicable to many active ingredients. Further, by adding the cross-linking agent before emulsification of the mixture, the step of adding the cross-linking agent and the step of diluting the mixture can be combined into one step.

(Isocyanate compound)
Any suitable isocyanate compound can be used in the method for producing polyurea microcapsules of the present disclosure as long as the isocyanate compound can produce polyurea microcapsules. The isocyanate compound has a structure O = C = N-RN = C = O. The isocyanate compound may be aromatic, aliphatic, linear, branched, or cyclic. In one embodiment, the isocyanate compound may have an average of 2 to 4 −N = C = O groups. In certain embodiments, the isocyanate compound comprises at least three isocyanate functional groups.

In one embodiment, the methods of making polyurea microcapsules of the present disclosure have one or more aromatic polyisocyanates and / or aliphatic polyisocyanates, or free isocyanate groups, with adducts, trimers and Use biuret or its derivatives, including combinations thereof. Examples of aromatic polyisocyanates include COSMONATE (registered trademark) M-100 (Mitsui Chemicals, Inc.), COSMONATE (registered trademark) M-200 (Mitsui Chemicals, Inc.), and COSMONATE (registered trademark) PH (Mitsui Chemicals, Inc.). ), Diphenylmethane diisocyanate such as COSMONATE (registered trademark) PH-G (Mitsui Chemicals, Inc.), and COSMONATE (registered trademark) T-65 (Mitsui Chemicals, Inc.), COSMONATE (registered trademark) T-80 (Mitsui Chemicals, Inc.) ), Toluene diisocyanate such as COSMONATE (registered trademark) T-100 (Mitsui Chemicals, Inc.) and the like. Examples of aliphatic polyisocyanates include TAKENATE (registered trademark) D-110N (Mitsui Chemicals, Inc.), TAKENATE (registered trademark) D-120N (Mitsui Chemicals, Inc.), and TAKENATE (registered trademark) D-131-N (registered trademark). Mitsui Chemicals, Inc.), TAKENATE (registered trademark) D-127N (Mitsui Chemicals, Inc.) and other xylylene diisocyanates, TAKENATE (registered trademark) D-160N (Mitsui Chemicals, Inc.), TAKENATE (registered trademark) D-165N (registered trademark) Hexamethylene diisocyanate such as Mitsui Chemicals, Inc., and isophorone diisocyanate such as TAKENATE (registered trademark) D-140N (Mitsui Chemicals, Inc.) can be mentioned.

(Crosslinking agent)
Crosslinkers are used to make the capsule walls of polyurea microcapsules. Amine can use polyurea microcapsules as a cross-linking agent in synthesis. Other cross-linking agents are guanidine and its salts, which are applied in the synthesis of microcapsules in the presence of catalysts. Examples of the cross-linking agent include guanidine carbonate, guanidine hydrochloride, guanidine nitrate, guanidine sulfate, guanidine acetate, guanidine salt containing guanidine phosphate and the like. The inorganic base may be used for pH adjustment, and examples of the inorganic base include alkali metal oxides such as sodium oxide, potassium oxide, calcium oxide, and cerium oxide, or alkaline earth metal oxides. Other polyamine cross-linking agents contain one or more NH ₂ groups per molecule and consist of tris (2-aminoethyl) amine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or a combination thereof.

In one embodiment, the method of making polyurea microcapsules of the present disclosure uses one or more cross-linking agents. In another embodiment, the guanidine carbonate is mixed with a surfactant and then with a solvent, an isocyanate compound, and an active ingredient. This procedure can easily reduce one step of adding a cross-linking agent after emulsification, which is common in conventional production methods.

By adding a cross-linking agent to the mixture of solvent, active ingredient, and isocyanate compound prior to emulsification, the polyurea microcapsules of the present disclosure are re-dispersible in water and not found in comparative production methods. Shows dispersibility. As long as the polyurea microcapsules of the present disclosure are produced using a cross-linking agent, an appropriate amount of the cross-linking agent can be used.

(Surfactant)
In one embodiment, the method for producing polyurea microcapsules of the present disclosure uses one or more surfactants. Examples of surfactants include anionic and nonionic surfactants. Specific examples of the anionic surfactant include poly (sodium 4-styrene sulfonate) (Mw-70,000 to 1,000,000) having different weight average molecular weights, and examples of the nonionic surfactant include poly (sodium 4-styrene sulfonate). , Polysorbate can be mentioned. Poly (sodium 4-styrene sulfonate) may have a weight average molecular weight of 70,000, 200,000, or 1,000,000. The molecular weight is the mass (gram) of 1 mole of the substance.

Any suitable amount of surfactant may be used as long as the polyurea microcapsules of the present disclosure can be made with surfactant. In one embodiment, the amount of surfactant is 0.5-10% by weight. In another embodiment, the amount of surfactant is 0.1-2%.

The amount of cross-linking agent can affect the dispersibility of the polyurea microcapsule powder in water. The higher the amount of guanidine carbonate, the better the dispersibility of the microcapsules in water is observed. The amount of cross-linking agent can also affect the redispersibility of polyurea microcapsules.

(solvent)
In one embodiment, the method of making polyurea microcapsules of the present disclosure uses one or more solvents. Any suitable solvent can be used as long as the active ingredient and the isocyanate compound are dissolved in the solvent to prepare a second mixture. Examples of solvents include glyceryl tributyrate, caprylic acid triglyceride, capric acid triglyceride, diethyl phthalate, dimethyl phthalate, methyl cocoate, and methyl cocoate or a combination thereof.

(Active ingredient)
In one embodiment, the method of making polyurea microcapsules of the present disclosure uses one or more active ingredients. Examples of active ingredients include insecticides and insect repellents. Specific examples of the active ingredient include paramentan-3,8-diol (CITREPEL® Chemian Technology Ltd, UK), eucalyptus oil, citronella oil (SIGMA ALDRICH®), geraniol oil, lemongrass oil, neem, basil. Examples thereof include oil, cedar oil, cinnamon oil, clove oil, castor oil, etofenprox, diiodomethyl-p-tolylsulfone (DMTS), 3-iodo-2-propynyl N-butylcarbamate (IPBC) and the like. Depending on the active ingredients contained in the microcapsules, the microcapsules are in the form of sprays, detergents, fabric softeners, laundry starch, shampoos, hair conditioners, body washes, hygiene products, paints, coatings, etc. It can be used to manufacture various final products such as mold products.

(Production method)
The polyurea microcapsules of the present disclosure are produced by the following methods. The first mixture is produced by mixing a surfactant solution with a cross-linking agent powder.

The second mixture is prepared by adding a solvent to the isocyanate compound followed by an active ingredient such as CITREPEL® which is a liquid. If the active ingredient is solid, the second mixture is made by adding the active ingredient to the solvent followed by the isocyanate compound.

The third mixture is produced by mixing the second mixture at a homogenization rate of 2,800 rpm until the addition of the second mixture to the first mixture is complete, for safety reasons. , These two solutions are not added at high homogenization rates. The third mixture is emulsified by increasing the homogenization rate at any temperature (eg, room temperature) for 2 minutes above 6,500 rpm.

The emulsified third mixture is cured at 55 ° C. for 2 hours with stirring.

The cured third mixture was subjected to the quantitative filter paper No. 1 manufactured by ADVATEC. Vacuum filter using 5C and wash with deionized water to remove unreacted chemicals and detergents.

The filtered third mixture is dried at room temperature for 2-5 hours.

The dried third mixture can be redispersed in water by adding water to the powder.

The fourth mixture is produced by adding a viscosity modifier to the dispersed third mixture.

(Viscosity modifier)
In one embodiment, the method for producing polyurea microcapsules of the present disclosure can use one or more viscosity modifiers. The dispersed third mixture is mixed with a viscosity modifier to make a fourth mixture. Examples of viscosity modifiers include xanthan gum, gum arabic, karaya gum, clay, starch polymers, colloidal polymers and the like.

The liquid on the right side of each photograph in FIG. 4 is a dispersion of polyurea microcapsules of the present disclosure and comparative poly after 2 minutes, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, and 6 hours. A redispersion of urea microcapsules. The liquid on the left side of each photograph in FIG. 4 is a dispersion of comparative polyurea microcapsules and comparative polyurea micro after 2 minutes, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, and 6 hours. It is a redispersion solution of capsules. Comparative polyurea microcapsules are produced by the method shown in FIG. Tris (2-aminoethyl) amine is used as a cross-linking agent. Comparative polyurea microcapsules are also produced using guanidine carbonate as a cross-linking agent by the method shown in FIG. Polyurea microcapsules produced by the method example shown in FIG. 19 using guanidine carbonate as a cross-linking agent could not be dispersed as shown in the comparative example of FIG.

As shown in FIG. 4, the polyurea microcapsules of the present disclosure can maintain a dispersed state in water for a longer period of time as compared with the comparative polyurea microcapsules. The polyurea microcapsules of the present disclosure can maintain a dispersed state in water for at least 15 minutes without sedimentation. After 6 hours, most of the particles settle to the bottom, but can be easily redispersed by shaking the mixture again. In other words, the polyurea microcapsules of the present disclosure are redispersible even 6 hours after dispersion. In contrast to the polyurea microcapsules of the present disclosure, comparative polyurea microcapsules are easily separated and not easily redispersed.

(Example 1)
Polyurea microcapsules are produced by the method shown in FIG. 20 ml of 1% poly (sodium 4-styrene sulfonate) (SIGMA ALDRICH®) and 0.4 g of guanidine carbonate (SIGMA ALDRICH®) were mixed in a first container at room temperature. A first mixture is made. In a second container, 6 g of glyceryl tributyrate (SIGMA ALDRICH®), 3 g of CITREPEL® as an active ingredient, and 1.2 g of TAKENATE® D-110N were mixed and the second container was mixed. Make a mixture of 2. The first mixture and the second mixture are mixed to make a third mixture. The third mixture is emulsified with a homogenizer (ULTRATURRAX, T25Basic, IKA) at 6,500 rpm for 2 minutes. The emulsified third mixture is stirred with a magnetic stirrer at room temperature at 450 rpm for 10 minutes. The third mixture is cured with stirring at 55 ° C. for 2 hours. The cured third mixture becomes a polyurea microcapsule slurry. The polyurea microcapsule slurry is filtered by suction using a vacuum filter (conventional method using a Buchner flask and a Buchner funnel). The filtered polyurea microcapsule slurry is placed on paper and dried at room temperature for 2-5 hours to give the polyurea microcapsule powder. 0.5 g of dried polyurea microcapsules are dispersed in 10 ml of water to prepare the sample (c) shown in FIG. Place the sample (c) in a 50 ml Falcon tube (polypropylene, BD Falcon ™).

(Example 2)
Polyurea microcapsules are produced by the method shown in FIG. 20 ml of 1% poly (sodium 4-styrene sulfonate) (SIGMA ALDRICH®) and 0.4 g of guanidine carbonate (SIGMA ALDRICH®) were mixed in a first container at room temperature. A first mixture is made. In a second container, 6 g of glyceryl tributyrate (SIGMA ALDRICH®), 3 g of CITREPEL® as an active ingredient, and 1.2 g of TAKENATE® D-110N were mixed and the second container was mixed. Make a mixture of 2. The first mixture and the second mixture are mixed to make a third mixture. The third mixture is emulsified with a homogenizer (ULTRATURRAX, T25Basic, IKA) at 6,500 rpm for 2 minutes. The emulsified third mixture is stirred with a magnetic stirrer at room temperature at 450 rpm for 10 minutes. The third mixture is cured with stirring at 55 ° C. for 2 hours. The cured third mixture becomes a polyurea microcapsule slurry. The polyurea microcapsule slurry is filtered by suction using a vacuum filter (eg, Buchner flask and Buchner funnel). The filtered polyurea microcapsule slurry is placed on paper and dried at room temperature for 2-5 hours to give the polyurea microcapsule powder. Disperse 0.5 g of dried polyurea microcapsules in 10 ml of water. 0.01 g of a powdery viscosity modifier (xanthan gum) is dissolved in 10 ml of water to prepare the sample (a) shown in FIG. 0.01 g of powdered viscosity modifier (gum arabic) is dissolved in 10 ml of water to prepare the sample (b) shown in FIG. The amount of the viscosity modifiers (xanthan gum and gum arabic) of the samples (a) and (b) is 0.1% by weight. Each sample (a) and (b) is placed in a 50 ml Falcon tube (polypropylene, BD Falcon ™).

As shown in FIG. 5, the dispersion characteristics of the sample (c) are compared with the dispersion characteristics of the samples (a) and (b). The dried polyurea microcapsule powder was dispersed in water by gently shaking, and its dispersibility was confirmed. The results are shown in FIG. The microcapsules dispersed in the xanthan gum solution have excellent stability and can maintain the microcapsules in a sufficiently dispersed state for 16 months or more.

(Example 3)
Polyurea microcapsules are produced by the method shown in FIG. 20 ml of 1% poly (sodium 4-styrene sulfonate) (SIGMA ALDRICH®) and 0.4 g of guanidine carbonate (SIGMA ALDRICH®) were mixed in a first container at room temperature. A first mixture is made. In the second container, 8 g of glyceryl tributyrate (SIGMA ALDRICH®), 1 g of etofenprox as an active ingredient, and 1.2 g of TAKENATE® D-110N are mixed, and the second container is mixed. Make a mixture. The first mixture and the second mixture are mixed to make a third mixture. The third mixture is emulsified with a homogenizer (ULTRATURRAX, T25Basic, IKA) at 6,500 rpm for 2 minutes. The emulsified third mixture is stirred at room temperature at 450 rpm for 10 minutes. The stirred third mixture is cured with stirring at 55 ° C. for 2 hours. The cured third mixture becomes a polyurea microcapsule slurry. The polyurea microcapsule slurry is filtered by suction using a vacuum filter (eg, Buchner flask and Buchner funnel). The filtered polyurea microcapsule slurry is placed on paper and dried at room temperature for 2-5 hours to give the polyurea microcapsule powder. Disperse 0.5 g of dried polyurea microcapsules in 10 ml of water.

(Example 4)
Polyurea microcapsules are produced by the method shown in FIG. 20 ml of 1% poly (sodium 4-styrene sulfonate) (SIGMA ALDRICH®) and 0.4 g of guanidine carbonate (SIGMA ALDRICH®) were mixed in a first container at room temperature. A first mixture is made. In the second container, 8 g of glyceryl tributyrate (SIGMA ALDRICH®), 1 g of etofenprox as an active ingredient, and 1.2 g of TAKENATE® D-110N are mixed, and the second container is mixed. Make a mixture. The first mixture and the second mixture are mixed to make a third mixture. The third mixture is emulsified with a homogenizer (ULTRATURRAX, T25Basic, IKA) at 6,500 rpm for 2 minutes. The emulsified third mixture is stirred at room temperature at 450 rpm for 10 minutes. The stirred third mixture is cured with stirring at 55 ° C. for 2 hours. The cured third mixture becomes a polyurea microcapsule slurry. The polyurea microcapsule slurry is filtered by suction using a vacuum filter (eg, Buchner flask and Buchner funnel). The filtered polyurea microcapsule slurry is placed on paper and dried at room temperature for 2-5 hours to give the polyurea microcapsule powder. Disperse 0.5 g of dried polyurea microcapsules in 10 ml of water. 0.01 g of viscosity modifier (powdered xanthan gum or powdered gum arabic) is dissolved in 10 ml of water containing 0.5 g of microcapsules.

The dispersion characteristics of the polyurea microcapsules dispersed in water (Example 3) are compared with the dispersion characteristics of the polyurea microcapsules dispersed in water using a viscosity modifier (xanthan gum and gum arabic) (Example 4). The microcapsules dispersed in the xanthan gum solution disperse well over time.

(Characteristic evaluation of polyurea microcapsules)
The feature evaluation of the polyurea microcapsules of the present disclosure is tested using different feature evaluation techniques.

(Shape / structure and other characteristics)
The shapes / structures of the polyurea microcapsules of the present disclosure are as shown in Fluorescent Optical Microscopy (FOM) as shown in FIG. 6, Optical Microscopy (OM) as shown in FIG. 7, and FIGS. 8 and 9. Detected by scanning electron microscopy (SEM). As shown in FIGS. 8 and 9, the polyurea microcapsules of the present disclosure are detected by SEM at different magnifications (1000x and 20,000x).

In the production method of Example 3, polyurea microcapsules are produced by the same method as in Example 3 except that 10 mg of coumarin-6 fluorescent dye (SIGMA ALDRICH®) is added to Etofenprox. Polyurea microcapsules are redispersed in water for fluorescence microscopy. A fluorescence optical microscope (FOM) of polyurea microcapsules encapsulating a coumarin-6 fluorescent dye is shown in FIG. FOM shows that almost all microcapsules are pigment-encapsulated. This demonstrates that efficient encapsulation of Etofenprox is performed by the methods of the present disclosure.

The OM of FIG. 7 shows good dispersion of the polyurea microcapsules in the dispersion, and the SEM shows information on the size and wall thickness of the polyurea microcapsules. The size of polyurea microcapsules is 10 to 50 microns. The wall thickness of polyurea microcapsules is 100-300 nm. The active ingredient content of polyurea microcapsules is 0.1 to 60% by weight.

(Encapsulation efficiency)
Encapsulation efficiency is determined by performing the content of Etofenprox by high performance liquid chromatography (HPLC) analysis. The dried polyurea microcapsules are produced by the production method disclosed in Example 3. 0.1 g of polyurea microcapsules were dispersed in 10 ml of acetonitrile in Sample 1. In Sample 1, 10% by weight of Etofenprox is contained in the acetonitrile. In Sample 2, 0.1 g of polyurea microcapsules were dispersed in 10 ml of acetonitrile. In Sample 2, 20% by weight of Etofenprox is contained in the acetonitrile. In Sample 3, 0.05 g of polyurea microcapsules were dispersed in 10 ml of acetonitrile. In Sample 3, 38% by weight of Etofenprox is contained in the acetonitrile. In Sample 4, 0.05 g of polyurea microcapsules were dispersed in 10 ml of acetonitrile. In Sample 4, 43% by weight of Etofenprox is contained in the acetonitrile. The microcapsules in acetonitrile for each sample are sonicated for 30 minutes to extract the entire core material. After sonication, each sample is filtered through a 0.45 micron membrane filter to remove wall material. The filtrate is injected into the HPLC using a DEVELOSIL® column. The results of HPLC are shown in Table 1. Table 1 shows that most etofenprox is encapsulated. This means that high encapsulation efficiency can be achieved with this manufacturing method of the present disclosure.

(Dispersion test)
The dispersion of the polyurea microcapsules of the present disclosure in water containing different viscosity modifiers is tested. Dispersion of the polyurea microcapsules of the present disclosure in commercially available paints, fabric softeners, starch and polyvinyl alcohol (PVA) is tested. Good dispersion is observed for a long time. As described in detail below, most commercial products contain thickeners and therefore no gum or other viscosity modifiers are added. Fluorescent dyes containing microcapsules are produced using CITREPEL® as an active ingredient, and the dispersion of microcapsules by UV irradiation is checked.

(Dispersion test-viscosity modifier)
The stable dispersion properties in water using xanthan gum and Karaya gum are compared with those in water microcapsules only (shown in FIG. 5). The amount of gum used is 0.1% by weight. The microcapsules containing xanthan gum have excellent stability and can keep the microcapsules in a sufficiently dispersed state for 5 months or more (16 months or more).

(Dispersion test-paint)
A method for producing dried polyurea microcapsules using Etofenprox is disclosed in Example 3, except that the active ingredient Etofenprox is changed to 0.1% comaline-6 fluorescent dye. It is the same as the one. Disperse 0.6 g of dried polyurea microcapsules of Example 3 in 10 g of paint: (ALES Anti-MosQ KANSAI PAINT® (Singapore) PteLTd.). One glass slide is painted with paint without the use of polyurea microcapsules. The two glass slides are painted with paint and polyurea microcapsules dispersed in the paint. Irradiate with ultraviolet rays (UV) using a penlight for several seconds (30 to 40 seconds). An optical microscope (OM) of these glass slides is observed as shown in FIG. The change in coloration after UV irradiation suggests that the polyurea microcapsules of the present disclosure are well dispersed in the paint. These results indicate the presence of well-dispersed microcapsules on the slide, and the change in color of the microcapsules demonstrates the presence of dye in the capsules.

The microcapsules used in these experiments are about 50 microns. This makes the surface of the slide rough, which can be seen from the darkfield image from FIG. From these results, good life of the paint can be achieved by changing the filling amount of Etofenprox.

(Dispersion test-softener)
The dispersion of the polyurea microcapsules of the present disclosure in a commercially available fabric softener is tested. Polyurea microcapsules are produced by the method of Example 3 except that the active ingredient etofenprox is replaced with 0.1% by weight CR-49 photochromic dye (Yamamoto Chemicals, Inc.).

The active ingredient, etofenprox, was changed to 0.1% photochromic dye microcapsules, and 10 g of the three softeners COMFORT® (Unilever), DOWNEY® (Procterand Gamble), and SOFTLAN®. 0.6 g of powdered polyurea microcapsules are produced by the method of Example 3, except that they are dispersed in (Colgate-Palmolive).

All three fabric softeners include fragrance capsules sized 5 to 20 microns. Shows good dispersion in all fabric softeners. The amount of the contents of the capsule is in the order of COMFORT (registered trademark)> DOWNEY (registered trademark)> SOFTLAN (registered trademark). In the case of COMFORT®, most of the large capsules observed under a light microscope (OM) (not shown) appear transparent. This may indicate that these capsules were empty at the time, indicating that the fragrance was completely released from the larger capsule.

The stability and compatibility of microcapsules is tested with fabric softener using microcapsules containing photochromic dyes. The results are shown in FIG. Powdered polyurea microcapsules are produced by the method of Example 3 except that the active ingredient etofenprox is changed to 0.1% by weight CR-49 photochromic dye (Yamamoto Chemicals, Inc.). The powdered microcapsules can be easily dispersed in the softener without adding a thickener, probably because these softeners have viscosity. 50 mg of dried microcapsules are dispersed in 5 ml of fabric softener without dilution. Each sample is placed in a 50 ml FALCON® tube (polypropylene, BD Falcon®). To confirm the dispersion of the microcapsules, UV light is applied to the softener through the tube using a UV penlight for 2-3 hours, 1 day, 5 days, 10 days, and 30 days. At least in COMFORT® and DOWNEY®, the viscosity of the softener under UV light (approximate wavelength is 365-375 nm) is high, so the dispersion of microcapsules is stable for 30 days or more without thinner. There is.

(Dispersion test-starch)
The dispersion of the polyurea microcapsules of the present disclosure in starch is tested. Powdered polyurea microcapsules are produced by the method of Example 3 except that the active ingredient etofenprox is changed to 0.1% by weight CR49 photochromic dye (Yamamoto Chemicals, Inc.).

For the sample shown on the left side of FIG. 12, 0.6 g of powdered polyurea microcapsules were dispersed in 10 g of powdered 3% starch (SIGMA ALDRICH®), and for the sample shown on the right side of FIG. Adds powdered 0.1% gum (SIGMA ALDRICH®) containing an aqueous solution before and after UV irradiation using UV penlight.

The microcapsules of the present disclosure dispersed in starch and gum exhibit better stability. The results before and after UV irradiation using the UV penlight are shown in FIG. Without the gum, the microcapsules of Example 3 settle after a few hours. As shown in FIG. 5, the stability of the dispersion is 16 months or longer in the presence of gum.

(Dispersion test-PVA)
The dispersibility of the polyurea microcapsules of the present disclosure in polyvinyl alcohol (PVA) is tested.

Powdered polyurea microcapsules are produced by the method of Example 3 except that the active ingredient etofenprox is changed to 0.1% by weight CR49 photochromic dye (Yamamoto Chemicals, Inc.). For sample 1 shown in the center of FIG. 13, 0.6 g of the powdered polyurea microcapsules of the present disclosure are dispersed in 10 g of polyvinyl alcohol (PVA) (DIASO, Japan). For sample 2 shown on the right side of FIG. 13, 0.01 g of powdered gum (SIGMA ALDRICH®) is added. PVA without microcapsules or gum is shown as a control on the left side of FIG.

The microcapsules of the present disclosure dispersed in PVA and gum show better stability than the microcapsules of the present disclosure dispersed only in PVA. After a few hours, the PVA-dispersed microcapsules show only low-intensity dye, whereas the gum-containing PVA-dispersed microcapsules show very good strength. These observations demonstrate that the microcapsules are well dispersed in PVA and PVA containing the gum solution. The results are shown in FIG. Between the sample containing microcapsules in PVA and the sample containing microcapsules in PVA containing gum, the sample containing microcapsules and gum exhibits better strength than the sample containing only microcapsules. These observations demonstrate that the microcapsules are more dispersed in the PVA containing the gum solution than in the PVA solution.

(Judicial disqualification test)
CITREPEL® in polyurea microcapsules produced by the method of the examples of the present disclosure dispersed in water with starch is applied to a cotton fabric (shown on the left side of FIG. 14). The powdered polyurea microcapsules are produced by the method of Example 1. Disperse 2.5 g of powdered polyurea microcapsules and 1.5 g of starch (REVIVENSTANTSTRACH, manufactured by Marico Limited) of the present disclosure in 50 ml of water. The mixture is applied to the fabric by immersing the cotton cloth in a starch solution containing microcapsules. The fabric shown on the left side of FIG. 14 is a cotton fabric with polyurea microcapsules. Add 1.5 g of starch (REVIVE INSTANT STARCH®, manufactured by Marico Limited) to 50 ml of water to make a control sample fabric. Water containing starch is applied to the fabric by immersing the cotton fabric in a starch solution. The fabric shown on the right side of FIG. 14 is a control fabric that does not contain polyurea microcapsules.

The test was performed at room temperature of 26.6 ° C. and relative humidity of 57%. As shown in FIG. 15, the cloth with polyurea microcapsules (sample) and the cloth without polyurea microcapsules (control example) are separately placed in an acrylic case (30 cubic centimeters). Fabric samples were prepared in tubes and placed on a hairless mouse wrapped in a wire mesh bag. Release 30 Aedes albopictus into each acrylic case. The survival rate of mosquitoes is measured for 10 minutes by counting the number of mosquito landings every 30 seconds. Only two landings were confirmed in control mice. Such a small number may be due to the effect of starch that hardens the fabric. Therefore, mosquito needles can hardly penetrate the cloth. In other words, more landings may be observed if the needle passes. On the other hand, no landing or bite was observed in the sample prepared using the polyurea microcapsules. Therefore, the sample clearly shows a 100% repellent effect. The test settings are shown in FIG.

(Knockdown test)
The knockdown test is performed on filter paper by brushing the starch with polyurea microcapsules containing Etofenprox. The test sample was prepared by encapsulating Etofenprox with a production medium such as starch or a solvent (for control) in a filter paper No. 12 × 15 cm in size. 1 (ADVANTEC®) is impregnated to produce.

The test system consists of healthy laboratory breeding susceptibility staining of adult female Aedes aegypti, 3-7 days old. The test system is bred in a colony room in the dark for 12 hours with a temperature of 28.2 ° C., a relative humidity of 70.10%, and 12-hour lighting (light bulb type and wattage or device name and manufacturer name, etc.).

(Sample 1-Left end of FIG. 16)
Powdered polyurea microcapsules are produced by the method of Example 3. 0.33 g of starch powder and 0.6 g of powdered polyurea microcapsules are added to 10 ml of water and the resulting mixture is dispersed by shaking. The content of Etofenprox is 0.6% by weight in solution.
(Sample 2-second on the left in FIG. 16)
0.33 g of starch powder is added to 10 ml of water and the resulting mixture is shaken to disperse. The content of Etofenprox is 0% by weight in solution.
(Sample 3-second on the right in Fig. 16)
0.06 g of Etofenprox is added to 10 ml of acetonitrile solvent and the resulting mixture is dispersed by shaking. The content of Etofenprox is 0.6% by weight in solution.
(Sample 4-Right end of FIG. 16)
Since the content of Etofenprox in the solution is 0% by weight, only the solvent is used.

Unencapsulated Etofenprox in solvent and encapsulated Etofenprox in polyurea microcapsules exhibit good knockdown properties against mosquitoes, as shown in FIG. Knockdown test condition 1 (left) for 3 samples, normal condition-no sample aging, condition 2 (center), acceleration condition 1-sample aging at 80 ° C for 2 days, condition 3 (right), acceleration condition 2 Tested for aging at −80 ° C. for 7 days.

Polyurea microcapsules containing starch exhibited both insecticidal and rapid knockdown effects on adult Aedes aegypti under three different conditions, usually 80 ° C. for 2 and 7 days of accelerated aging. Accelerated aging of paper impregnated with unencapsulated Etofenprox shows significantly lower mortality. On the other hand, paper impregnated with polyurea microcapsules and starch after accelerated aging for 2 and 7 days showed complete biomortality.

High mortality in accelerated conditions is achieved by encapsulated etofenprox in polyurea microcapsules, suggesting a long-lasting effect compared to unencapsulated etofenprox in solvent.

FIG. 17 shows another aspect of the present disclosure. In FIG. 17, the method for producing a mosquito repellent is a step of mixing a surfactant and a cross-linking agent to prepare a first mixture and a step of adding an active ingredient and an isocyanate compound to a solvent to prepare a second mixture. A step of mixing the first mixture with the second mixture to prepare a third mixture, a step of emulsifying the third mixture, a step of curing the emulsified third mixture, and a cured first. It includes a step of filtering the mixture of 3, a step of drying the filtered third mixture, and a step of mixing the dried third mixture with water and starch to prepare a mosquito repellent.

FIG. 18 shows yet another embodiment of the present disclosure. In FIG. 18, the mosquito repellent method includes a step of applying a mosquito repellent to the fabric and a step of covering the skin protected by the fabric. The mosquito repellent is produced by the method shown in FIG.

The mosquito repellents of the present disclosure may be included in detergents, fabric softeners, laundry starches, ironing waters, shampoos, hair conditioners, body washes, hygiene products, paints, or coatings.

This disclosure is an example, and various changes can be made by adding, modifying, or deleting details without departing from the fair scope of the teachings contained in this disclosure. Accordingly, the present disclosure is not limited to the particular details of the present disclosure, except to the extent that the following claims are necessarily so limited:

This application claims priority under Singapore Patent Application No. 10201880631V filed July 13, 2018, the contents of which are incorporated herein.

Claims (26)

A step of mixing a surfactant and a cross-linking agent to prepare a first mixture, and
The step of adding the active ingredient and the isocyanate compound to the solvent to prepare a second mixture, and
A step of mixing the first mixture with the second mixture to prepare a third mixture, and
The step of emulsifying the third mixture and
A step of curing the emulsified third mixture and
The step of filtering the cured third mixture and
A method for producing polyurea microcapsules, which comprises a step of drying the filtered third mixture. The method according to claim 1, further comprising the step of dispersing the dried third mixture in water to prepare a fourth mixture. The method according to claim 2, further comprising a step of adding a viscosity modifier to the fourth mixture to prepare a fifth mixture. Any one of claims 1 to 3, wherein the surfactant comprises poly (sodium 4-styrene sulfonate), which is an anionic surfactant having a weight average molecular weight of 70,000 or more and 1,000,000 or less. The method described in. The cross-linking agent
Guanidine salt,
The method according to any one of claims 1 to 4, which comprises an alkali metal oxide or an alkaline earth metal oxide, or _{a polyamine cross-linking agent containing one or more NH 2 groups per molecule.} The guanidine is selected from the group consisting of guanidine carbonate, guanidine hydrochloride, guanidine nitrate, guanidine sulfate, guanidine acetate, and guanidine phosphate.
The alkali metal is selected from the group consisting of sodium and potassium.
The alkaline earth metal oxide is selected from the group consisting of calcium and cerium.
The method of claim 5, wherein the polyamine cross-linking agent is selected from the group consisting of tris (2aminoethyl) amine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. The active ingredients are paramentan-3,8-diol, eucalyptus oil, citronella oil, gelaniol oil, lemongrass oil, neem, basil oil, cypress oil, cinnamon oil, clove oil, castor oil, etofenprox, diiodomethyl-p. The method according to any one of claims 1 to 6, which comprises-trill sulfone, 3-iodo-2-propynyl N-butyl carbamate, or a combination thereof. Any one of claims 1 to 7, wherein the solvent comprises glyceryl tributyrate, caprylic acid triglyceride, capric acid triglyceride, diethyl phthalate, dimethyl phthalate, methyl cocoate, methyl cocoate, or a combination thereof. The method described in. The isocyanate compound is an aromatic polyisocyanate, an aliphatic polyisocyanate, or a derivative of an aromatic polyisocyanate or an aliphatic polyisocyanate having a free isocyanate group and containing an addition compound, a trimer, biuret, or a combination thereof. The method according to any one of claims 1 to 8, which comprises. The ninth aspect of the present invention, wherein the aliphatic polyisocyanate contains xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or a combination thereof, and the aromatic polyisocyanate contains toluene diisocyanate, diphenylmethane diisocyanate, or a combination thereof. the method of. The aromatic polyisocyanates are COSMONATE® M-100, COSMONATE® M-200, COSMONATE® PH, COSMONATE® PH-G, COSMONATE® T-65, COSMONATE® T-80, COSMONATE® T-100 or a combination thereof, the aliphatic polyisocyanate is TAKENATE® D-110N, TAKENATE® D-120N, TAKENATE. (Registered Trademark) D-160N, TAKENATE (Registered Trademark) D-140N, TAKENATE (Registered Trademark) D-131-N, TAKENATE (Registered Trademark) D-127N, TAKENATE (Registered Trademark) D-165N, or a combination thereof. The method according to claim 9 or 10, wherein the method comprises. The method of claim 3, wherein the viscosity modifier comprises xanthan gum, gum arabic, karaya gum, clay, starch polymer, colloidal polymer or a combination thereof. A step of mixing a surfactant and a cross-linking agent to prepare a first mixture, and
The step of adding the active ingredient and the isocyanate compound to the solvent to prepare a second mixture, and
A step of mixing the first mixture with the second mixture to prepare a third mixture, and
The step of emulsifying the third mixture and
A step of curing the emulsified third mixture and
The step of filtering the cured third mixture and
Polyurea microcapsules produced by a method comprising the step of drying the filtered third mixture. The polyurea microcapsules according to claim 13, wherein the surfactant is poly (sodium 4-styrene sulfonate) having a weight average molecular weight of 70,000 or more and 1,000,000 or less. The cross-linking agent
Guanidine salt,
The polyurea microcapsules according to claim 13 or 14, comprising an alkali metal oxide or an alkaline earth metal oxide, or _{a polyamine cross-linking agent containing one or more NH 2 groups per molecule.} The guanidine is selected from the group consisting of guanidine carbonate, guanidine hydrochloride, guanidine nitrate, guanidine sulfate, guanidine acetate, and guanidine phosphate.
The alkali metal is selected from the group consisting of sodium and potassium.
The alkaline earth metal oxide is selected from the group consisting of calcium and cerium.
The polyurea microcapsule according to claim 15, wherein the polyamine cross-linking agent is selected from the group consisting of tris (2aminoethyl) amine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. The active ingredients are paramentan-3,8-diol, eucalyptus oil, citronella oil, gelaniol oil, lemongrass oil, neem, basil oil, cypress oil, cinnamon oil, clove oil, castor oil, etofenprox, diiodomethyl-p. The polyurea microcapsule according to any one of claims 13 to 16, which comprises-tolylsulfone, 3-iodo-2-propynyl N-butylcarbamate, or a combination thereof. 13. The polyurea microcapsules described. The isocyanate compound is an aromatic polyisocyanate, an aliphatic polyisocyanate, or a derivative of an aromatic polyisocyanate or an aliphatic polyisocyanate having a free isocyanate group and containing an addition compound, a trimer, a biuret, or a combination thereof. The polyurea microcapsule according to any one of claims 13 to 18, which comprises. The polyurea micro according to claim 19, wherein the isocyanate contains xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or a combination thereof, and the aromatic polyisocyanate contains toluene diisocyanate, diphenylmethane diisocyanate, or a combination thereof. capsule. The aromatic polyisocyanates are COSMONATE® M-100, COSMONATE® M-200, COSMONATE® PH, COSMONATE® PH-G, COSMONATE® T-65, COSMONATE® T-80, COSMONATE® T-100 or a combination thereof, the aliphatic polyisocyanate is TAKENATE® D-110N, TAKENATE® D-120N, TAKENATE. (Registered Trademark) D-160N, TAKENATE (Registered Trademark) D-140N, TAKENATE (Registered Trademark) D-131-N, TAKENATE (Registered Trademark) D-127N, TAKENATE (Registered Trademark) D-165N, or a combination thereof. The polyurea microcapsule according to claim 19 or 20, which comprises. A step of mixing a surfactant and a cross-linking agent to prepare a first mixture, and
The step of adding the active ingredient and the isocyanate compound to the solvent to prepare a second mixture, and
A step of mixing the first mixture with the second mixture to prepare a third mixture, and
The step of emulsifying the third mixture and
A step of curing the emulsified third mixture and
The step of filtering the cured third mixture and
The step of drying the filtered third mixture and
A method for producing a mosquito repellent, which comprises a step of mixing the dried third mixture with water and starch to prepare a mosquito repellent. The step of applying the mosquito repellent produced by the method according to claim 22 to the fabric, and
A method of repelling mosquitoes, comprising the step of covering the skin to be protected with the fabric. A consumer product comprising the polyurea microcapsule according to any one of claims 13 to 21, wherein the consumer product is a detergent, fabric softener, laundry glue, ironing water, shampoo, hair conditioner, body. Consumer products, including washes, sanitary products, paints, coatings, or combinations thereof. The antifungal product containing the polyurea microcapsule according to any one of claims 13 to 21, wherein the antifungal product is a detergent, a fabric softener, a starch, a shampoo, a hair conditioner, a body wash, and a hygiene. Antifungal products, including supplies, paints, coatings, or combinations thereof. A mosquito repellent product containing the polyurea microcapsule according to any one of claims 13 to 21, wherein the mosquito repellent product is a detergent, fabric softener, laundry glue, ironing water, shampoo, hair conditioner. Mosquito repellent products, including body wash, hygiene products, paints, coatings, or combinations thereof.

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