WO2020149684A2

WO2020149684A2 - Biodegradable capsule with safety due to no irritation to human body and manufacturing method therefor

Info

Publication number: WO2020149684A2
Application number: PCT/KR2020/000834
Authority: WO
Inventors: 김현; 조경인; 차승환; 김정표; 종민호; 양동연
Original assignee: 주식회사 대하맨텍
Priority date: 2019-01-18
Filing date: 2020-01-16
Publication date: 2020-07-23
Also published as: WO2020149684A3

Abstract

The present invention relates to: a biodegradable capsule which is a capsule having a form in which a capsule wall surrounds fragrance or oil, wherein a polymer, formed by the reaction of a fibrous natural polymer, a natural protein polymer, an aliphatic polyesterpolyol, an aliphatic crosslinking agent, an aqueous natural surfactant solution, and amino acids, constitutes the capsule wall of the capsule, and the capsule has the diameter of 0.1-300 µm; and a manufacturing thereof. According to the present invention, since a polymer, formed by the reaction of a fibrous natural polymer with excellent biodegradability, a natural protein polymer, an aliphatic polyesterpolyol, an aliphatic crosslinking agent, an aqueous natural surfactant solution, and amino acids, constitutes a capsule wall to form a capsule, a capsule that has no irritation to the human body and is also biodegradable can be manufactured.

Description

Safe and biodegradable capsule with no irritation to human body and its manufacturing method

The present invention relates to a biodegradable capsule and a method for manufacturing the same, and more specifically, by reacting a fibrous natural polymer having excellent biodegradability, a natural protein polymer, an aliphatic polyester polyol, an aliphatic crosslinking agent, an aqueous solution of a natural surfactant, and an amino acid. It relates to a capsule capable of biodegrading without irritation to the human body by forming a capsule by forming a capsule wall of the formed polymer, and a method for manufacturing the same.

Plastic materials are used in all areas of our daily life, from disposable packaging materials, toys, and automotive interior materials to everyday materials. These plastic materials have made our lives convenient and enriched in a short period of time, but despite a short period of time, they cause various environmental problems. Among them, the destruction and pollution of the marine ecosystem of plastic, which has recently become a major issue, causes millions of tons of plastic waste to flow into the sea every year, and is not broken down, broken into pieces, combined with toxic substances, accumulated in the sea, swallowed by plankton and small fish, and then sea. Riding on the food chain, he finally reached a point serious enough to have a detrimental effect on people. Accordingly, environmental groups have emphasized the need to regulate the use of plastics, and countries are introducing laws to regulate the use of plastics. Also, many companies are making efforts to replace plastic straws or cups with paper materials to reduce plastic use, or to replace synthetic plastic scrubs used in cosmetics and toothpaste with natural scrubs such as coffee grounds and grain flour.

Although most capsules are different from general plastic materials in physicochemicals, the synthetic process becomes difficult to decompose or turns into a material with a slow decomposition rate, which increases the possibility of causing environmental pollution.

Therefore, it is required to develop biodegradability of capsules that are frequently used as a useful means to effectively protect and facilitate the use of functional substances in the fields of household goods and cosmetics, and to develop materials that are safe for the human body.

To realize this, many microencapsulation technologies have been developed, but the functionality as a capsule is reduced depending on only natural products, a crosslinking agent that is very harmful to the human body, such as glutaraldehyde, or a synthetic material is used, or the biodegradability is very low. Processes that are complex, use organic solvents, and are difficult to mass-produce are methods that have low or lack biodegradability, safety, functionality, and economy.

[Advanced technical literature]

[Patent Document]

Republic of Korea Registered Patent Publication No. 10-1366307

The problem to be solved by the present invention is to easily disintegrate by microorganisms or enzymes, and use natural fibrous polymers, natural protein polymers, amino acids, and naturally occurring surfactant aqueous solutions, which are human-friendly materials, and realize the functionality of capsules more efficiently. In order to provide a biodegradable capsule and a method for manufacturing the biodegradable capsule, which is excellent in biodegradability, safe for the human body, and effectively functional, by using a small amount of a biodegradable aliphatic polyester polyol and an aliphatic crosslinking agent.

The present invention is a capsule having a form in which the capsule wall surrounds a fragrance or an oil, wherein a natural polymer of fibers, a natural protein polymer, an aliphatic polyester polyol, an aliphatic crosslinking agent, an aqueous solution of natural surfactant, and a polymer formed by reacting amino acids It forms a capsule wall of the capsule, the capsule provides a biodegradable capsule characterized in that it has a diameter of 0.1 ~ 300㎛.

The fibrous natural polymer is methyl cellulose, ethyl ether cellulose, ethyl-2-hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxy Hydroxybutyl methylcellulose, 2-aminoethyl 2-hydroxypropyl cellulose, hemicellulose, 6-carboxy cellulose, carboxymethyl cellulose, carboxymethyl ether cellulose, cellulose acetate, alginate and sorbitol. Can.

The natural protein polymer is hydrolyzed oat protein, hydrolyzed corn protein, hydrolyzed yeast protein, hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed rice protein, hydrolyzed potato protein , Hydrolyzed silk protein, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed elastin, hydrolyzed casein, lauridmonium hydroxypropyl hydrolyzed wheat protein, lauridmonium hydrad Hydroxypropyl hydrolyzed soy protein, lauryldimonium hydroxypropyl hydrolyzed collagen, myristoyl hydrolyzed collagen, oliboyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, TA-Cocoil Hydrolyzed Collagen, Potassium Unsylenoyl Hydrolyzed Collagen, Potassium Cocoyl Hydrolyzed Collagen, Potassium Palmitoyl High-Rolyzed Wheat Protein, Hydroxypropyl Trimonium Hydrolyzed Silk and It may include one or more substances selected from the group consisting of hydroxypropyl trimonium hydrolyzed collagen.

The aliphatic polyester polyol is adipic acid, azelaic acid, chloric acid, chloric anhydride, fumaric acid, isophthalic acid, maleic anhydride, phthalic anhydride, succinic acid, succinic anhydride, sebacic acid, diglycolic acid, terephthalic anhydride , Citric acid, trimellitic acid, trimellitic anhydride, one or more acids selected from the group consisting of itaconic acid and citraconic acid, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol, neo At least one alcohol selected from the group consisting of pentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methylglucoside, dipentaerythritol and sorbitol And an aliphatically unsaturated polyester polyol obtained by esterification dehydration and condensation reaction of the liver.

The aliphatic crosslinking agent is one selected from the group consisting of 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. It may contain the above substances.

The natural surfactant aqueous solution is disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, decyl polyglucoside, alkyl poly Glucoside, babasumidopropylbetaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alaninate, lauryl glucoside, palm kernel-cocoglucoside, decyl glucoside, sodium cocoyl glutamate and potassium coco It may be an aqueous solution containing one or more substances selected from the group consisting of monoglycinate.

The amino acids include glycine, alanine, proline, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, lysine, histidine, arginine, aspartic acid and glutamic acid. It may include one or more substances selected from the group consisting of.

In addition, the present invention, (a) a fragrance or oil, and the step of mixing a natural natural polymer with a fiber, a natural protein polymer, and an aliphatic polyester polyol, (b) a flavor or oil, a natural natural polymer with a fiber, natural Mixing an aliphatic crosslinking agent in a mixture of a protein polymer and an aliphatic polyester polyol, and (c) mixing and emulsifying an aqueous solution of a natural surfactant in the mixture in which the aliphatic crosslinking agent is mixed to form an oil/water emulsion. And (d) adding an amino acid to the oil/water emulsion and reacting to obtain a capsule.

The fibrous natural polymer is preferably mixed with 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil.

The natural protein polymer is preferably 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil.

The aliphatic polyester polyol is preferably mixed with 1 to 5 parts by weight based on 100 parts by weight of a perfume or oil.

The aliphatic crosslinking agent is preferably mixed in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of a fragrance or oil, and the aliphatic crosslinking agent is 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexanedi It may include one or more substances selected from the group consisting of isocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

The natural-derived surfactant aqueous solution may be an aqueous solution made by mixing 1 to 10 parts by weight of a natural-derived surfactant with respect to 100 parts by weight of a fragrance or oil and adding 10 to 90 parts by weight of water with respect to 100 parts by weight of a fragrance or oil.

The natural surfactants include disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, decyl polyglucoside, alkylpolyglucoside , Barbasuamidopropyl betaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alaninate, lauryl glucoside, palm kernel-cocoglucoside, decyl glucoside, sodium cocoyl glutamate and potassium cocoyl It may include one or more substances selected from the group consisting of glycinate.

The amino acid is preferably mixed with 0.1 to 5 parts by weight based on 100 parts by weight of the fragrance or oil.

In the step (c) or (d), the pH of the oil/water emulsion can be adjusted with an acid or a base.

In the step (d), the reaction is preferably carried out at a temperature of 30 to 50 ℃.

According to the present invention, a polymer formed by reacting a fibrous natural polymer having excellent biodegradability, a natural protein polymer, an aliphatic polyester polyol, an aliphatic crosslinking agent, an aqueous solution derived from a natural surfactant, and an amino acid forms a capsule wall to form a capsule in the human body. Biodegradable capsules can be prepared without irritation. Aliphatic polyester polyol that can be easily degraded by microorganisms or enzymes, and uses human-friendly fibrous natural polymers, natural protein polymers, natural-derived aqueous surfactant solutions, and amino acids, as well as to more effectively realize the functionality of capsules. By using a small amount of an aliphatic crosslinking agent, a biodegradable capsule that is excellent in biodegradability, safe for the human body, and can effectively use functionality can be prepared.

In addition, according to the present invention, by using a small amount of biodegradable aliphatic polyester polyol and an aliphatic crosslinking agent and reacting at a relatively low temperature of 30 to 50° C., the functionality of the capsule is more effectively realized and side effects arising in the production process are prevented and produced. Improve the efficiency of.

1 is a view showing a biodegradable capsule according to a preferred embodiment of the present invention.

The biodegradable capsule according to a preferred embodiment of the present invention is a capsule having a form in which the capsule wall surrounds a fragrance or an oil, a fibrous natural polymer, a natural protein polymer, an aliphatic polyester polyol, an aliphatic crosslinking agent, and a naturally occurring surfactant The polymer formed by the reaction of the aqueous solution and the amino acid forms the capsule wall of the capsule, and the capsule has a diameter of 0.1 to 300 μm.

A method for preparing a biodegradable capsule according to a preferred embodiment of the present invention includes: (a) mixing a perfume or oil, a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol; and (b) a perfume or oil. And, a step of mixing an aliphatic crosslinking agent in a mixture of a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol, and (c) mixing and emulsifying an aqueous solution of a natural surfactant in the mixture in which the aliphatic crosslinking agent is mixed. Forming an oil/water emulsion and (d) adding an amino acid to the oil/water emulsion and reacting to obtain a capsule.

Hereinafter, preferred embodiments according to the present invention will be described in detail. However, the following embodiments are provided to those of ordinary skill in the art to fully understand the present invention and may be modified in various other forms, and the scope of the present invention is limited to the embodiments described below. It does not work.

In the description or claims of the present invention, when any one component "includes" another component, it is not limited to being interpreted as being composed of the component only, unless specifically stated otherwise, and other components are further added. It should be understood that it can be included.

Hereinafter, a method of manufacturing a biodegradable capsule according to a preferred embodiment of the present invention will be described in more detail.

The present invention provides a biodegradable capsule that is excellent in biodegradability, safe for the human body, and can effectively use functionality, and a method for manufacturing the same.

Referring to Figure 1, the biodegradable capsules according to a preferred embodiment of the present invention, the capsule wall 10 is a capsule having a form surrounding the fragrance or oil 20, a fibrous natural polymer, natural protein polymer, aliphatic The polymer formed by the reaction of a polyester polyol, an aliphatic crosslinking agent, an aqueous solution of a natural surfactant, and an amino acid forms the capsule wall 10 of the capsule, and the capsule has a diameter of 0.1 to 300 μm.

The natural surfactant aqueous solution is disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, decyl polyglucoside, alkyl poly Glucoside, babasumidopropylbetaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alanate, lauryl glucoside, palm kernel-coco glucoside (condensation of palm kernel acid and coconut acid with glucose It may be an aqueous solution containing one or more substances selected from the group consisting of compounds), decyl glucoside, sodium cocoyl glutamate and potassium cocoyl glycinate.

In order to prepare a biodegradable capsule according to a preferred embodiment of the present invention, a fragrance or oil, a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol are mixed.

The fragrance may be a substance such as aroma herb fragrance, rose fragrance, jasmine fragrance, lavender fragrance, mint fragrance, banana fragrance, apple fragrance, strawberry fragrance, vanilla fragrance, mixtures thereof, and the like.

The oil may be one or more substances selected from the group consisting of natural oil, synthetic oil, and oily oil. The natural oil may be jojoba oil, olive oil, rose hip oil, camellia oil, argan oil, avocado oil, coconut oil, almond oil, tea tree oil, eucalyptus oil, rosemary oil, lavender oil, mixtures thereof, and the like. The synthetic oil may be ester oil, silicone oil, or a mixture thereof. The oily oil may be a material used as a cosmetic raw material such as retinol, ceramide, ethylhexyl salicylate, ethylhexyl methoxycinnamate, alpha-bisabolol, oil-soluble licorice extract, mixtures thereof, and the like.

The fibrous natural polymer is preferably mixed with 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil. The fibrous natural polymer is a linear chain polysaccharide polymer compound in which hundreds to thousands of glucose units are connected by glycoside bonds, and since it has excellent reactivity with other compounds, it stabilizes the substance to be supported in the capsule due to the polymer formed after the reaction. There is an advantage that biodegradation can be easily performed by microorganisms or enzymes existing in nature after the capsule is applied to the product and used. This makes it easy to control the reactivity and biodegradability of the capsules by containing natural fibers of fiber.

The natural protein polymer is preferably 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil. The natural protein polymer is a form capable of hydrolyzing a protein having a high molecular weight and dissolving it in water, and is preferably selected from natural protein polymers having low crystallinity and flexibility due to irregular repeating units, which are advantageous for biodegradation compared to synthetic polymers. Do.

The aliphatic polyester polyol is preferably mixed with 1 to 5 parts by weight based on 100 parts by weight of a perfume or oil. The aliphatic polyester polyol has hydrophobicity and hydrophilicity, and the active site is in the molecular chain and structurally flexible, so it is an excellent biodegradable polymer, and it compensates for the disadvantages of weak physical strength and low uniformity of natural protein polymers. Therefore, when the capsule is applied to the product, the capsule is not destroyed, and when the product to which the capsule is applied is easily destroyed by physical force, a useful substance having a function can be effectively released.

It is preferable that the aliphatic polyester polyol is an aliphatic unsaturated polyester polyol obtained by an esterification dehydration condensation reaction between a divalent or higher acid and a dihydric or higher alcohol. For example, the aliphatic polyester polyol is adipic acid, azelaic acid, chloric acid, chloric anhydride, fumaric acid, isophthalic acid, maleic anhydride, phthalic anhydride, succinic acid, succinic anhydride, sebacic acid, diglycolic acid, Terephthalic anhydride, citric acid, trimellitic acid, trimellitic anhydride, one or more acids selected from the group consisting of itaconic acid and citraconic acid, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol , Neopentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methyl glucoside, dipentaerythritol and sorbitol It may be an aliphatic unsaturated polyester polyol obtained by esterification dehydration and condensation reaction between alcohols.

An aliphatic crosslinking agent is mixed with a mixture of a perfume or oil, a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol.

The aliphatic crosslinking agent is preferably mixed in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of a perfume or oil. The aliphatic crosslinking agent can form part of a polymer material based on polyester that is structurally flexible and has better biodegradability than polyether, and increases the strength of the capsule while increasing the strength of the capsule while using a significantly less amount than when forming a general plastic material. It is possible to control the release of the useful oily substance and to reduce the reaction time, thereby ensuring functionality and economy.

A mixture of the aliphatic cross-linking agent is mixed with a natural-derived aqueous surfactant solution and emulsified to form an oil/water emulsion (Oil/Water, O/W or Oil in Water). At this time, the pH can be adjusted with acid or base. The pH is preferably adjusted to pH 3 to 5 when acidic conditions are required and pH 9 to 11 when basic conditions are required depending on the isoelectric point or properties of the substance. Protein and amino acid-based substances have an isoelectric point where the charge of the ionic amino acid present in the substance changes depending on the pH, so that the ionicity changes and solubility and reactivity changes, which can affect the reaction conditions of the capsule and compatibility with other substances. Therefore, it is necessary to adjust the pH according to the compound to be blended.

An oil/water (O/W or oil in water) emulsion is formed by the emulsification. The mixing may use a homomixer or the like, it is preferable to perform at a speed of about 1000 ~ 5000rpm.

The natural surfactant aqueous solution is an aqueous solution made by mixing 1 to 10 parts by weight of a natural derived surfactant with respect to 100 parts by weight of a perfume or oil and adding 10 to 90 parts by weight of water with respect to 100 parts by weight of a perfume or oil to solubilize it. It is preferred. Naturally-derived surfactants have a structure that is advantageous for biodegradation and are bio-friendly compared to synthetic surfactants, so they are safe and have additional functions such as moisturizing and conditioning.

The natural surfactants include disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, decyl polyglucoside, alkylpolyglucoside , Babasuamidopropylbetaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alanate, lauryl glucoside, palm kernel-coco glucoside (condensation of palm kernel acid and coconut acid with glucose) Compound obtained), decyl glucoside, sodium cocoyl glutamate, and potassium cocoyl glycinate.

Amino acids are added to the oil/water emulsion and reacted to obtain capsules. At this time, the pH can be adjusted with acid or base. The pH is preferably adjusted to pH 3 to 5 when acidic conditions are required and pH 9 to 11 when basic conditions are required depending on the isoelectric point or properties of the substance. The reaction is preferably carried out at a temperature of 30 to 50 ℃. Protein and amino acid-based substances have an isoelectric point where the charge of the ionic amino acid present in the substance changes depending on the pH, so that the ionicity changes and solubility and reactivity changes, which can affect the reaction conditions of the capsule and compatibility with other substances. Therefore, it is necessary to adjust the pH according to the compound to be blended. The reaction is preferably performed while stirring at a rate of about 300 to 500rpm. The reaction time is cured over time to form a capsule wall, and finally a biodegradable capsule is formed.

The amino acid is preferably mixed with 0.1 to 5 parts by weight based on 100 parts by weight of the fragrance or oil. Amino acids are low-molecular substances that do not require a hydrolysis process and have little interference with side chains, so they are easily exhibited by microorganisms, and are more easily degraded by microorganisms. Can increase. In addition, due to the presence of an amino group, it is possible to form a solid capsule wall with good reactivity, thereby facilitating the release control of fragrances or oils and enabling low-temperature reaction and shortening of the reaction time.

The reaction is preferably carried out at a temperature of 30 to 50 ℃. The reaction at a low temperature can prevent side reactions and deformation of the polymer material that may occur at a high temperature reaction, and it is possible to efficiently encapsulate a material having high oxidation or volatility.

The capsules manufactured in this way are excellent in biodegradability, are safe for the human body, can more effectively implement the functionality of the capsule, prevent side effects occurring in the production process, and improve production efficiency.

According to the present invention, the fibrous natural polymer, natural protein polymer, aliphatic polyester polyol, aliphatic cross-linking agent, natural surfactant aqueous solution and a polymer formed by reacting amino acids form a capsule wall of the capsule to provide excellent biodegradability, safety and functionality. It is possible to manufacture a biodegradable capsule that is easy to protect and use a substance (perfume or oil).

The biodegradable capsules produced by the present invention are fibrous natural polymers, natural protein polymers, aliphatic polyester polyols, aliphatic crosslinking agents, natural surfactant aqueous solutions and polymers formed by reacting amino acids to form a capsule wall of the capsule for flavoring or Oil is protected.

Hereinafter, embodiments according to the present invention are specifically presented, and the present invention is not limited by the following embodiments.

In a 500 ml beaker, 100 g of aromatic herbs, 10 g of methyl cellulose, 10 g of hydrolyzed wheat protein, and 2 g of aliphatic polyester polyol obtained by esterifying and dehydrating condensation reaction of adipic acid and 1,3 butylene glycol are uniformly mixed and prepared in advance. After adding 1 g of the prepared isophorone diisocyanate, an aqueous solution of natural surfactant made by mixing 5 g of natural-derived surfactant, Baba-sumidopropylbetaine and 45 g of water, was added, and a homomixer was used at a rate of 3,000 rpm. The mixture was stirred for 20 minutes to prepare an oil/water emulsion.

After adding the oil/water emulsion to a 1L 4-neck flask, adding a small amount of caustic soda to adjust the pH to 9-11, adding 0.5 g of aspartic acid, adjusting the reaction temperature to 40°C, and then about 3 A biodegradable capsule was prepared by reacting with stirring for an hour.

In a 500 ml beaker, 100 g of aromatic herbs, 10 g of methyl cellulose, 10 g of hydrolyzed oat protein, and 2 g of an aliphatic polyester polyol obtained by esterifying and dehydrating condensation of adipic acid and pentanediol are uniformly mixed, and isophorone prepared in advance After additionally mixing 1 g of diisocyanate, a natural-derived surfactant aqueous solution made by mixing 5 g of natural-derived surfactant, Baba-sumidopropylbetaine and 45 g of water, was added and stirred for about 20 minutes at a rate of 3,000 rpm using a homomixer. To prepare an oily/aqueous emulsion.

After adding the oil/water emulsion to a 1L 4-neck flask, adding a small amount of acetic acid to adjust the pH to 3~5, adding 1.5g of arginine, adjusting the reaction temperature to 40°C and stirring for about 3 hours While reacting, a biodegradable capsule was prepared.

In a 500 ml beaker, 100 g of aroma herbal perfume, 10 g of methyl cellulose, 10 g of laurimmonium hydroxypropyl hydrolyzed wheat protein, and 2 g of an aliphatic polyester polyol obtained by esterifying and decondensation reaction of adipic acid and sorbitol are uniformly mixed, After additionally mixing 1 g of isophorone diisocyanate prepared in advance, a natural-derived surfactant aqueous solution made by mixing 5 g of natural-derived surfactant, Baba-sumidopropylbetaine and 45 g of water, was added, and a homomixer was used to speed up 3,000 rpm. It was stirred for about 20 minutes with an oil/water emulsion.

The oil/water emulsion was added to a 1 liter 4-neck flask, and a small amount of acetic acid was added to adjust the pH to 3 to 5, glutamine 1.5g was added and the reaction temperature was adjusted to 40°C, followed by stirring for about 3 hours. By reacting to prepare a biodegradable capsule.

In a 1L 4-neck flask, 10 g of melamine, 40 g of distilled water, 20 g of 35 wt% aqueous formaldehyde solution and a small amount of sodium hydroxide were added to adjust the pH to 8-10, and stirred at 80°C for 30 minutes to melamine-formaldehyde prepolymer. Was prepared.

Ethylene-maleic acid copolymer resin (trade name: EMA-31, manufactured by Monsanto Co., Ltd.) 5 wt% in a separate 1 liter beaker to prepare 200 g of an emulsifier acting as an anionic surfactant, and 100 g of aroma herb fragrance is added thereto to add a homomixer The mixture was stirred at a speed of 3,000 rpm for about 20 minutes to prepare an oil/water emulsion.

After mixing the melamine-formaldehyde prepolymer and the oil/water emulsion, the mixture was stirred at 70° C. for about 3 hours to cure the capsule wall, thereby preparing a melamine capsule.

50 g of food starch (substitution rate 0.005) substituted with octenyl was dissolved in 50 g of water. In order to increase the density of starch in this solution, 5 g of NaCl was added to prepare an aqueous solution of starch dissolved in a single phase.

The starch aqueous solution was added with 100 g of aroma herb fragrance, and emulsified by stirring at a high speed of 3000 rpm for 20 minutes with a homomixer.

5 g of glutaraldehyde serving as a crosslinking agent was added to a solution of emulsifying the aroma herb fragrance in the starch aqueous solution, and a capsule was prepared by crosslinking at 3000 rpm for 40 minutes.

Each capsule prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 was evaluated for biodegradability, fracture irritation, and scenting performance.

[Biodegradability measurement method and criteria]

KS I ISO 9408 for measuring the aerobic final biodegradability of organic compounds in a liquid medium by measuring the oxygen demand of the water quality-sealed respiratory measuring system for each capsule prepared in Examples 1 to 3 and Comparative Examples 1 to 2 and the same. The standards were evaluated using the OECD 301F method.

Specifically, it is shown in Table 1 as follows according to the biodegradability measurement.

○: The biodegradability value is 60% or more compared to the reference substance.

△: Biodegradability value is more than 30% to less than 60% compared to the reference substance

Ⅹ: Biodegradability value is less than 30% of the reference substance

[Skin irritation test method and evaluation criteria]

Each capsule prepared in Examples 1 to 3 and Comparative Examples 1 to 2 was applied to 31 subjects on the back for 24 hours, and then observed after 30 minutes, 24 hours, and 48 hours of removal of the patch, followed by the International Society for Contact Dermatology (ICDRG) and According to the standards applied by the American Cosmetics Association (PCPC) standards, it is evaluated as non-irritating/low-stimulating/light-stimulating/medium-stimulating/strong-stimulating and shown in Table 1.

[Test Method and Evaluation Criteria for Diffraction Performance]

Each of the capsules prepared in Examples 1 to 3 and Comparative Examples 1 to 2 was added 0.5% to the base having no fragrance, and the towel was washed according to the standard usage of the high concentration of fiber concentrate, and then dried at room temperature for 24 hours. A scent diffusing performance evaluation sample was prepared.

The evaluation of the scenting performance was performed on 30 capsules of each capsule prepared in Examples 1 to 3 and Comparative Examples 1 to 2, and the produced towels were rubbed five times with each hand, and the sensory sensitivity to the odor felt by the nose was measured. After evaluating and evaluating with 1 to 5 points (5 points: very strong, 4 points: strong, 3 points: normal, 2 points: slightly weak, 1 point: weak, 0 points: none) The final evaluation was performed (150 to 101 points: good, 100 to 51 points: normal, 50 to 0: bad).

평가 항목Evaluation item	실시예 1Example 1	실시예 2Example 2	실시예 3Example 3	비교예 1Comparative Example 1	비교예 2Comparative Example 2
생분해도Biodegradability	○○	○○	○○	XX	△△
피부자극Skin irritation	무자극Irritation	무자극Irritation	무자극Irritation	저자극Hypoallergenic	중자극Stimulation
발향성능Scenting performance	좋음good	좋음good	좋음good	보통usually	나쁨Bad

As shown in Table 1, Examples 1 to 3 were evaluated as capsules having excellent biodegradability and excellent biodegradability due to no skin irritation compared to Comparative Examples 1 to 2.

In addition, it was found that the scent-repellent performance of Examples 1 to 3 is superior to that of the capsules of Comparative Examples 1 to 2, so that perfumes or oils can be used most effectively.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art.

According to the present invention, the polymer formed by reacting the fibrous natural polymer having excellent biodegradability, natural protein polymer, aliphatic polyester polyol, aliphatic crosslinking agent, an aqueous solution of natural surfactant, and amino acid forms a capsule wall to form a capsule in the human body. Biodegradable capsules can be prepared without irritation, and there is industrial applicability.

Claims

A capsule having a form in which the capsule wall surrounds the fragrance or oil,

The fibrous natural polymer, the natural protein polymer, the aliphatic polyester polyol, the aliphatic crosslinking agent, the natural surfactant aqueous solution and the polymer formed by the reaction of amino acids form the capsule wall of the capsule,

The capsule is a biodegradable capsule, characterized in that it has a diameter of 0.1 to 300㎛.
The method of claim 1, wherein the fibrous natural polymer is methyl cellulose, ethyl ether cellulose, ethyl-2-hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl cellulose, hydroxy 1 selected from the group consisting of hydroxypropyl methyl cellulose, hydroxybutyl methylcellulose, 2-aminoethyl 2-hydroxypropyl cellulose, hemicellulose, 6-carboxy cellulose, carboxymethyl cellulose, carboxymethyl ether cellulose, cellulose acetate, alginate and sorbitol. Biodegradable capsules, characterized in that it contains more than one species.
The method of claim 1, wherein the natural protein polymer is hydrolyzed oat protein, hydrolyzed maize protein, hydrolyzed yeast protein, hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed rice protein, Hydrolyzed potato protein, hydrolyzed silk protein, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed elastin, hydrolyzed casein, lauridmonium hydroxypropyl hydrolyzed wheat protein , Laurodimonium hydroxypropyl hydrolyzed soy protein, lauryl dimonium hydroxypropyl hydrolyzed collagen, myristoyl hydrolyzed collagen, oliboyl hydrolyzed wheat protein, cocodimonium hydroxypropyl Hydrolyzed wheat protein, T-Co-coil Hydrolyzed collagen, Potassium unsilenoyl hydrolyzed collagen, Potassium cocoyl hydrolyzed collagen, Potassium palmitoyl high-rolled wheat protein, Hydroxypropyl trimonium A biodegradable capsule comprising one or more substances selected from the group consisting of hydrolyzed silk and hydroxypropyltrimonium hydrolyzed collagen.
According to claim 1, wherein the aliphatic polyester polyol is adipic acid, azelaic acid, chloric acid, chloric anhydride, fumaric acid, isophthalic acid, maleic anhydride, phthalic anhydride, succinic acid, succinic anhydride, sebacic acid, Diglycolic acid, terephthalic anhydride, citric acid, trimellitic acid, trimellitic anhydride, one or more acids selected from the group consisting of itaconic acid and citraconic acid, and ethylene glycol, propylene glycol, 1,3-butylene Group consisting of glycol, pentanediol, neopentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methylglucoside, dipentaerythritol and sorbitol Biodegradable capsules, characterized in that it comprises an aliphatic unsaturated polyester polyol obtained by esterification dehydration condensation reaction between one or more alcohols selected from.
The method of claim 1, wherein the aliphatic crosslinking agent is 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Biodegradable capsules, characterized in that it comprises at least one substance selected from the group consisting of.
The method of claim 1, wherein the aqueous solution of natural surfactant is disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, Decyl polyglucoside, alkyl polyglucoside, babasumidopropyl betaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alanate, lauryl glucoside, palm kernel-coco glucoside, decyl glucoside, sodium Biodegradable capsules, characterized in that the aqueous solution containing at least one substance selected from the group consisting of cocoyl glutamate and potassium cocoyl glycinate.
The method of claim 1, wherein the amino acid is glycine, alanine, proline, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, lysine, histidine, arginine, A biodegradable capsule comprising one or more substances selected from the group consisting of aspartic acid and glutamic acid.
(a) mixing a perfume or oil, a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol;

(b) mixing an aliphatic crosslinking agent in a mixture of a perfume or oil, a fibrous natural polymer, a natural protein polymer, and an aliphatic polyester polyol;

(c) mixing an emulsified natural surfactant aqueous solution and emulsifying the mixture of the aliphatic crosslinking agent to form an oil/water emulsion; And

(d) A method for preparing a biodegradable capsule, comprising adding an amino acid to the oil/water emulsion and reacting to obtain a capsule.
The method of claim 8, wherein the fibrous natural polymer is mixed with 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil,

The fibrous natural polymer is methyl cellulose, ethyl ether cellulose, ethyl-2-hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxy Containing at least one substance selected from the group consisting of hydroxybutyl methylcellulose, 2-aminoethyl 2-hydroxypropyl cellulose, hemicellulose, 6-carboxy cellulose, carboxymethyl cellulose, carboxymethyl ether cellulose, cellulose acetate, alginate and sorbitol Method of manufacturing a biodegradable capsule, characterized in that.
The method of claim 8, wherein the natural protein polymer is mixed with 1 to 20 parts by weight based on 100 parts by weight of fragrance or oil,

The natural protein polymer is hydrolyzed oat protein, hydrolyzed corn protein, hydrolyzed yeast protein, hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed rice protein, hydrolyzed potato protein , Hydrolyzed silk protein, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed elastin, hydrolyzed casein, lauridmonium hydroxypropyl hydrolyzed wheat protein, lauridmonium hydrad Hydroxypropyl hydrolyzed soy protein, lauryldimonium hydroxypropyl hydrolyzed collagen, myristoyl hydrolyzed collagen, oliboyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, TA-Cocoil Hydrolyzed Collagen, Potassium Unsylenoyl Hydrolyzed Collagen, Potassium Cocoyl Hydrolyzed Collagen, Potassium Palmitoyl High-Rolyzed Wheat Protein, Hydroxypropyl Trimonium Hydrolyzed Silk and Method for producing a biodegradable capsule comprising one or more substances selected from the group consisting of hydroxypropyltrimonium hydrolyzed collagen.
The method of claim 8, wherein the aliphatic polyester polyol is mixed with 1 to 5 parts by weight based on 100 parts by weight of fragrance or oil,

The aliphatic polyester polyol is adipic acid, azelaic acid, chloric acid, chloric anhydride, fumaric acid, isophthalic acid, maleic anhydride, phthalic anhydride, succinic acid, succinic anhydride, sebacic acid, diglycolic acid, terephthalic anhydride , Citric acid, trimellitic acid, trimellitic anhydride, one or more acids selected from the group consisting of itaconic acid and citraconic acid, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol, neo At least one alcohol selected from the group consisting of pentyl glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, methylglucoside, dipentaerythritol and sorbitol A method for producing a biodegradable capsule comprising an aliphatically unsaturated polyester polyol obtained by an esterification dehydration reaction of liver.
The method according to claim 8, wherein the aliphatic crosslinking agent is mixed with 0.1 to 5 parts by weight based on 100 parts by weight of the fragrance or oil,

The aliphatic crosslinking agent is one selected from the group consisting of 4,4'-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Method for producing a biodegradable capsule comprising the above substances.
The method of claim 8, wherein the aqueous solution of natural surfactant is mixed with 1 to 10 parts by weight of natural surfactant with respect to 100 parts by weight of perfume or oil, and 10 to 90 parts by weight of water with respect to 100 parts by weight of perfume or oil. It is an aqueous solution made,

The natural surfactants include disodium laureth sulfosuccinate, cocamidopropyl betaine, lauramidopropyl betaine, sodium polyethylene glycol-7 olive oil carboxylate, sodium cocoyl apple amino acid, decyl polyglucoside, alkylpolyglucoside , Barbasuamidopropyl betaine, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium cocoyl alaninate, lauryl glucoside, palm kernel-cocoglucoside, decyl glucoside, sodium cocoyl glutamate and potassium cocoyl Method for producing a biodegradable capsule comprising at least one substance selected from the group consisting of glycinate.
The method of claim 8, wherein the amino acid is mixed with 0.1 to 5 parts by weight based on 100 parts by weight of fragrance or oil,

The amino acids include glycine, alanine, proline, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, serine, threonine, cysteine, asparagine, glutamine, lysine, histidine, arginine, aspartic acid and glutamic acid. Method for producing a biodegradable capsule comprising at least one substance selected from the group consisting of.
The method of claim 8, wherein in step (c) or step (d), the pH of the oil/water emulsion is adjusted with an acid or a base.
The method of claim 8, wherein in the step (d), the reaction is performed at a temperature of 30-50°C.