WO2018034364A1 - Microsponge having enhanced solubility control and redissolution properties - Google Patents
Microsponge having enhanced solubility control and redissolution properties Download PDFInfo
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- WO2018034364A1 WO2018034364A1 PCT/KR2016/009093 KR2016009093W WO2018034364A1 WO 2018034364 A1 WO2018034364 A1 WO 2018034364A1 KR 2016009093 W KR2016009093 W KR 2016009093W WO 2018034364 A1 WO2018034364 A1 WO 2018034364A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
Definitions
- the present invention relates to a microsponge with improved solubility control and re-dissolution properties, and more particularly, to a water-soluble or water-dispersible disintegrant which has a water-soluble polymer material as a matrix component and can control solubility and improve re-dissolution properties. It relates to a microsponge containing.
- a molded product in the form of a microsponge is a step of preliminarily freezing a temperature gradient parallel to the thickness direction inside the solution or gel by cooling the interface side with the air layer of the water-soluble polymer material or the gel, and preliminary freezing thereof. It is prepared through a process of freeze-drying the solution or gel of the frozen water-soluble polymer material.
- the molded product in the form of a micro sponge is used in various fields such as cosmetics, foods, especially health supplements, medicines such as wound dressings, oral disintegrating agents, industrial products having aroma and deodorant, and industrial products such as pesticides and fertilizers. have.
- the microsponge-type lyophilized products include natural polymers such as collagen or hyaluronic acid as matrix components.
- Collagen sponges having no network bonds are prepared from collagen aqueous solution by lyophilization or mixed with water. It is manufactured by removing water from the collagen lumps foamed using, and in particular, a collagen sponge having a crosslinked structure is known to be stable in water (Patent Document 1).
- the hyaluronic acid microsponge prepared by adding an epoxy-based crosslinking agent to the hyaluronic acid solution to hydrogel, and then expanded to give porosity, and then lyophilized the expanded hyaluronic acid hydrogel to control the pore size. It could be applied as a support (patent document 2).
- the collagen or hyaluronic acid-based non-crosslinked microsponge has a disadvantage in that the mechanical strength is poor or it is difficult to control the dissolution rate when contacted with water.
- the mechanical strength is poor or it is difficult to control the dissolution rate when contacted with water.
- cross-linked microsponge can be expected to improve the mechanical strength, there is a property that does not re-dissolve in water, there is a limitation in the application.
- Patent Document 3 there is a known method of adjusting the solubility by controlling the pores by pre-freeze drying and electroporation control method, but there is a problem that the manufacturing process is complicated and the economic cost is accompanied by an increase in the production cost (Patent Document 3).
- the inventors of the present invention have a water-soluble natural polymer or a synthetic polymer as a matrix component, and if a water-soluble or water-dispersible disintegrant is included therein to form a lyophilized microsponge-shaped molded article, water is kept in water while maintaining mechanical strength.
- the present invention has been completed by focusing on the fact that not only the solubility can be controlled, but also the microsponge having remarkably improved re-dissolution properties when contacted with water.
- Patent Document 1 Korean Laid-Open Patent Publication No. 10-2007-0064329
- Patent Document 2 Korean Patent Publication No. 10-2007-0108062
- Patent Document 3 International Publication WO 2001/057121
- the present invention has been made in view of the above problems, and an object of the present invention is to control the solubility, to easily control the density and strength of the sponge, not only to excellent re-dissolution characteristics, but also without adding a preservative. It is also to provide a micro sponge having a long-term storage and distribution stability.
- the present invention for achieving the above object is a water-soluble polymer material; And a water-soluble or water-dispersible disintegrant.
- the water-soluble polymer material is beta glucan, hyaluronic acid, hydroxypropylmethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, chitosan, gelatin, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyacrylamide, xanthan gum, polymer It is characterized by at least one member selected from the group consisting of collagen, carrageenan, pullulan, pectin, chondroitin sulfate, dextran and alginic acid.
- the content of the water-soluble polymer material is characterized in that 0.1 to 50% by weight based on the micro sponge.
- the water-soluble disintegrant is a low molecular weight carboxymethyl cellulose, low molecular weight hydroxypropyl methyl cellulose, low molecular weight hydroxyethyl cellulose, low molecular weight chitin, low molecular weight chitosan, low molecular weight collagen, low molecular weight polyacrylic acid, low molecular weight polyacrylamide, low It is characterized by at least one member selected from the group consisting of molecular weight polyvinyl alcohol and low molecular weight polyethylene oxide.
- the water-soluble disintegrant is characterized in that at least one selected from the group consisting of glucose, sucrose, maltose and lactose.
- the water-soluble disintegrant is one selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, hydroxypropyl cyclodextrin, hydroxyethyl cyclodextrin, carboxymethyl cyclodextrin, methyl cyclodextrin and glucosyl cyclodextrin. It is characterized by the above.
- the water dispersible disintegrant is characterized in that at least one selected from microcolloidal silica, nanoclay, titanium oxide, talc, or mica inorganic particles, or organic particles of acrylic powder, nylon powder, polyethylene powder or polypropylene powder.
- the weight ratio of the water-soluble polymer material and the water-soluble or water-dispersible disintegrant in the micro sponge is characterized in that 1: 0.5 to 100.
- the microsponge is characterized in that it further comprises a functional imparting material.
- the microsponge is characterized in that it further comprises one or more additives selected from the group consisting of surfactants, colorants, flavors, sweeteners, oils, waxes and antioxidants.
- microsponge is characterized in that it is in the form of a sphere or a sheet can be formulated in a spherical, heart-shaped, tablet form or sheet form.
- the micro-sponge prepared according to the present invention can control the solubility, control the density and strength of the sponge, not only excellent re-dissolution characteristics, but also excellent long-term storage and distribution stability without adding a preservative.
- Formulated in spherical, heart, tablet or sheet form it can be applied to food, medicine, quasi-drugs, cosmetics, household goods, animal drugs, pesticides and industrial products.
- FIG. 1 is a schematic diagram showing the collapse of the sponge according to the manufacture and re-dissolution of the micro-sponge according to the present invention.
- Figure 2 is a photograph observing the state of hydration of the microsponge prepared from Example 1 of the present invention.
- Figure 3 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Example 1 of the present invention.
- Figure 4 is a photograph observing the state of hydration of the microsponge prepared from Comparative Example 1 of the present invention.
- Figure 5 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Comparative Example 1 of the present invention.
- Figure 6 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Comparative Example 2 of the present invention.
- Figure 7 is a photograph observing the state of hydration of the microsponge prepared from Example 3 of the present invention.
- SEM scanning electron microscope
- the present invention is a water-soluble polymer material; And a water-soluble or water-dispersible disintegrant.
- beta glucan as a matrix component of the micro sponge, beta glucan, hyaluronic acid, hydroxypropylmethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, chitosan, gelatin, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, and polyacryl Amide, xanthan gum, polymeric collagen, carrageenan, pullulan, pectin, chondroitin sulfate, dextran and alginic acid are used.
- the water-soluble polymer material is conventionally used at room temperature or when heated to dryness. The thing of the high molecular weight which has film-like or blocky strength is preferable.
- the content of the water-soluble polymer material is preferably 0.1 to 50% by weight, and more preferably 0.2 to 30% by weight with respect to the micro sponge. At this time, if the content of the water-soluble polymer material is less than 0.1% by weight with respect to the micro sponge, the content as a matrix component is too low may decrease the mechanical strength of the micro sponge, the content of the water-soluble polymer material is 50% by weight relative to the micro sponge If exceeded, the content of the water-soluble or water-dispersible disintegrant is relatively low, and there is a concern that the re-solubility of the micro sponge is lowered when contacted with water.
- the present invention serves to improve the dissolution rate when reducing the viscosity of the water-soluble polymer solution as a matrix component in the process of manufacturing the micro sponge or redissolved in the water again to the water-soluble or water dispersible It is characterized by including a disintegrant.
- low molecular weight carboxymethyl cellulose low molecular weight hydroxypropylmethyl cellulose, low molecular weight hydroxyethyl cellulose, low molecular weight chitin, low molecular weight chitosan, low molecular weight collagen, low molecular weight polyacrylic acid, low molecular weight polyacrylamide, low molecular weight At least one selected from the group consisting of molecular weight polyvinyl alcohol and low molecular weight polyethylene oxide is used.
- a water-soluble polymer may be used as long as it has a high solubility in water and a dissolution rate in a fibrous, pulp, powder or solid state having a constant crystal structure at room temperature or when heated to dryness.
- the water-soluble disintegrant may be one or more selected from the group consisting of glucose, sucrose, maltose and lactose, and may be a low molecular sugar that is powder or crystals upon drying.
- the water-soluble disintegrant is selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, hydroxypropyl cyclodextrin, hydroxyethyl cyclodextrin, methyl cyclodextrin, carboxymethyl cyclodextrin and glucosyl cyclodextrin.
- the water dispersible disintegrant at least one selected from microcolloidal silica, nanoclay, titanium oxide, talc, mica inorganic particles or organic particles such as acrylic powder, nylon powder, polyethylene powder or polypropylene powder, In order to improve the dispersibility or surface properties of the inorganic particles or organic particles, inorganic particles or organic particles surface-treated with organic or inorganic components may be used.
- the water-soluble disintegrant or water-dispersible disintegrant may be used alone or in combination, but the weight ratio of the water-soluble polymer material and the water-soluble or water-dispersible disintegrant in the micro sponge is 1: 0.5 to 100 with the solubility of the micro sponge. Density and strength can be easily adjusted, it is preferable to maximize the re-dissolution properties when in contact with water, and more preferably 1: 1 to 30.
- cyclodextrin and its derivatives, and organic or inorganic compound-treated porous beads such as porous silica
- the microsponge disintegrates in water and re-dissolves, it can show its efficacy by slowly releasing the impregnated functional impregnated substances, and these sustained-release functions are cosmetics, medicines, deodorants, household goods including fragrances, pesticides and fertilizers. It can be widely used for industrial products, such as these.
- the present invention may further include a functional imparting substance in the microsponge, wherein the functional imparting substance, when redissolved, is released and exhibits a function, a whitening agent, an anti-depressant agent, a sunscreen agent, a moisturizer, a humectant, a release agent, and an anti-aging agent.
- Agents anti-wrinkle agents, weight loss agents, weight gain agents, ingredients that improve elasticity, ingredients that stimulate collagen or elastin synthesis, anti acne agents, anti-inflammatory agents, antioxidants, anti-free radical ingredients, pro-colorants, or bleaching
- the properties of the functional imparting substance are water-soluble, poorly soluble, oil-soluble, or water-dispersible, and may be oil or waxy.
- an oil- or wax-like functional imparting substance in order to contain an oil- or wax-like functional imparting substance, without using a conventional method such as micro-encapsulation or emulsification, it is dispersed in an aqueous solution of the matrix component and the disintegrant and frozen, and then lyophilized to obtain an oil- or wax-like phase.
- a microsponge having a functional imparting substance stably included in the pores of the sponge is obtained.
- the microsponge according to the present invention has one technical feature of having long-term storage and distribution stability without adding a preservative, it is possible to feel a preservative such as a preservative, or color, aroma, and taste as necessary.
- the micro sponge may further include at least one additive selected from the group consisting of a surfactant, a colorant, a flavoring agent, a sweetener, an antioxidant, and a preservative, so that the physical properties of the microsponge during re-dissolution are further included. Is given.
- the microsponge may shrink or expand according to the design of the container used in the freeze-drying process and the characteristics of the raw material after freeze-drying, surface properties and colors may be changed, and the spherical, heart-shaped, tablet-type or It is obtained in the form of a sheet or a sheet which can be formulated in a sheet form.
- the microsponge according to the present invention forms pores with a uniform cross-sectional shape as well as the surface layer, and scans that the water-soluble polymer material, which is a matrix component, and the water-soluble or water-dispersible disintegrant, are uniformly present in the form of a sponge as one material. It was confirmed by an electron microscope (SEM). Furthermore, when hydrated in water, disintegrants, which dissolve or disperse rapidly in water as they rapidly enter the pores by capillary action, first dissolve or disperse rapidly and induce the internal penetration of water much faster. It was confirmed that the water-soluble polymer material, which is a matrix component, was continuously hydrated and dissolved in a sufficient amount of water so as to disintegrate / dissolve at a very high rate.
- the molded article on the micro-sponge prepared by the conventional water-soluble solid agent has a similar structure, but in the case of the micro sponge made of only the water-soluble solid agent, water is rapidly introduced into the pores by capillary action as in the micro sponge of the present invention.
- the viscosity rises rapidly to prevent further water from flowing into or transferred to the water-soluble solid agent, which takes a long time until the water-soluble solid agent is hydrated in water and completely dissolved. If you do not dissolve by rubbing or stirring or shaking the container by hydrating the water again with physical force, it is difficult to dissolve completely.
- Figure 1 shows a schematic diagram showing the collapse of the sponge according to the manufacture and re-dissolution of the micro-sponge according to the present invention.
- beta glucan 0.5 wt%, which is a water-soluble polymer
- 3 g of marine collagen low molecular weight collagen
- 5 g of water-soluble oligo chitosan low molecular weight chitosan
- the mixed solution was placed in a spherical mold having a diameter of 11 mm, placed in a low temperature freezer, and frozen at -40 ° C. for 1 hour.
- the frozen balls were removed from the mold and placed in a freeze dryer in an exposed state to dry for 24 hours to prepare a microsponge.
- Microsponge was prepared in the same manner as in Example 1, except that 30 g of aqueous solution of beta glucan (1% by weight) and 70 g of aqueous solution of sodium hyaluronate (0.5% by weight) were used to obtain a mixed solution using 2 g of beta cyclodextrin and 2 g of marine collagen. Prepared.
- aqueous beta glucan solution (1 wt%) and 80 g of aqueous sodium hyaluronate solution (0.5 wt%) were mixed and stirred to obtain a mixed solution.
- 2 g of hydroxypropyl cyclodextrin and 2 g of marine collagen powder mixture were prepared, and 0.5 g of shea butter was added to an oil mixture of 1 g of rosehip oil and 1 g of tocopherol to dissolve the shea butter at 70 ° C.
- the oil mixture was then poured into a mixture of hydroxypropyl cyclodextrin and marine collagen powder to form a dough, which was then dispersed again in a mixed solution of aqueous beta glucan solution and aqueous sodium hyaluronate solution.
- a microsponge was prepared from the dispersion solution in the same manner as in Example 1.
- a microsponge was prepared in the same manner as in Example 1 only from an aqueous sodium hyaluronate solution in which 1 g of sodium hyaluronate was dissolved in 100 g of water.
- Microsponge was prepared in the same manner as in Example 1 only from beta glucan aqueous solution in which 1 g of beta glucan was dissolved in 100 g of water.
- Figure 2 shows a photograph observing the hydration state of the micro-sponge prepared from Example 1 of the present invention, as shown in Figure 2, time after dropping the prepared ball-type microsponge in water Therefore, even though no external force is applied, the pores formed by lyophilization are rapidly introduced into the pores by capillary action, and at the same time, the disintegrant (disintegrant) melts and the microsponge disintegrates rapidly.
- Example 3 shows a scanning electron microscope (SEM) photograph of the microsponge prepared in Example 1 of the present invention, wherein the water-soluble polymer material and the water-soluble disintegrant do not phase separate from each other to form a uniform wall of the cell. In addition, it can be confirmed that the gap of the regular cells is formed.
- Figure 4 shows a photograph observing the state of hydration of the microsponge prepared from Comparative Example 1 of the present invention, as shown in Figure 4, the time after dropping the prepared ball-shaped microsponge in water As the elapsed time, the outside is hydrated and dissolved to some extent, but as time passes, the hydration rate is slowed down, and eventually, it takes a considerable time to completely dissolve unless physical external force is applied from the outside.
- FIG. 5 and 6 show scanning electron microscope (SEM) images of microsponges prepared from Comparative Examples 1 and 2 of the present invention, respectively.
- the microsponges prepared from Comparative Example 1 were relatively uniform cells. It can be seen that it has a structure, but in the case of the microsponge manufactured from Comparative Example 2, the pores are well formed, while the cell wall has an excessively thin and coarse structure to hydrate well, but the structure is fragile enough to handle. You can check that you have it.
- Figure 7 shows a photograph observing the hydration state of the microsponge prepared from Example 3 of the present invention, the content of the oil component as a functional imparting substance not included in the microsponge prepared from Example 1 High, despite the structure of the oil dispersed in the pores of the sponge, hydroxypropyl cyclodextrin used as a water-soluble disintegrant and low-molecular weight of marine collagen was rapidly hydrated to confirm that it collapses at almost the same rate as in Example 1 Can be. Therefore, it can be seen again that water-soluble disintegrants play an important role in re-dissolving the sponge in water.
- Example 8 shows a scanning electron microscope (SEM) photograph of the microsponge prepared in Example 3 of the present invention, in which oil components which are not dissolved in water are uniformly dispersed in the uniformly formed pores. I can confirm that there is.
- Table 1 shows the re-dissolution time for each hydration solution of the microsponges prepared from Examples 1 to 4 and Comparative Examples 1 and 2, and the feeling of use when applying the skin thereof.
- Cosmetic composition 10 parts butylene glycol, 3 parts glycerin, 0.3 parts sebum / fiji-17 / 6 copolymer, 0.2 parts sebum-75 0.2 parts, xanthan gum, 1 part sebum-60 hydrogenated caster 0.3 parts of oil, 0.1 parts of disodium ethane, 1 part of sodium hyaluronate, 3 parts of chamomile flower / leaf extract, 0.5 parts of sage extract, 0.5 parts of lavender extract, 3 parts of rosemary leaf extract, 0.8 parts of phenoxyethanol, 0.3 parts of fragrances and 76 parts of purified water
- the microsponge prepared from Examples 1 to 4 of the present invention is significantly shorter re-dissolution time, even if the hydration solution is water or cosmetics compared to the micro sponge prepared in Comparative Example 1 (Comparative Example 2 It has a fragile structure that cannot be handled, so it is not applicable to skin dissolution time because it is not applicable), and it can be seen that it has excellent feeling when applying skin.
- the microsponge produced from the present invention was confirmed to be excellent in long-term storage and distribution stability even when no conventional preservatives are included.
- the micro-sponge prepared according to the present invention can control the solubility, easy to control the density and strength of the sponge, excellent re-dissolution properties, excellent long-term storage and distribution stability without addition of preservatives Therefore, it is possible to apply to food, pharmaceuticals, quasi-drugs, cosmetics, household goods, animal medicines, pesticides and industrial products in the form of sphere, heart, tablet or sheet.
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Abstract
Description
본 발명은 용해도 조절 및 재용해 특성이 향상된 마이크로스펀지에 관한 것으로, 보다 상세하게는 수용성 고분자 소재를 매트릭스 성분으로 하고, 용해도 조절이 가능하며 재용해 특성을 향상시킬 수 있는 수용성 또는 수분산성 붕해제를 포함하는 마이크로스펀지에 관한 것이다.The present invention relates to a microsponge with improved solubility control and re-dissolution properties, and more particularly, to a water-soluble or water-dispersible disintegrant which has a water-soluble polymer material as a matrix component and can control solubility and improve re-dissolution properties. It relates to a microsponge containing.
일반적으로 마이크로스펀지 형태의 성형체는, 수용성 고분자 소재의 용액 또는 겔의 공기층과의 계면 측을 냉각함으로써 그 용액 또는 겔의 내부에 두께방향과 평행한 온도구배를 발생시키고 예비동결 하는 공정과, 그 예비동결한 수용성 고분자소재의 용액 또는 겔을 동결건조 하는 공정을 통하여 제조된다. 이렇게 해서 제조된 마이크로스펀지 형태의 성형체는 화장품, 식품 특히 건강보조 식품, 창상피복재, 구강내 붕괴 제제와 같은 의약품, 방향 및 소취작용이 있는 생활용품, 농약 및 비료 등의 공산품 등 다양한 분야에 이용되고 있다.Generally, a molded product in the form of a microsponge is a step of preliminarily freezing a temperature gradient parallel to the thickness direction inside the solution or gel by cooling the interface side with the air layer of the water-soluble polymer material or the gel, and preliminary freezing thereof. It is prepared through a process of freeze-drying the solution or gel of the frozen water-soluble polymer material. The molded product in the form of a micro sponge is used in various fields such as cosmetics, foods, especially health supplements, medicines such as wound dressings, oral disintegrating agents, industrial products having aroma and deodorant, and industrial products such as pesticides and fertilizers. have.
상기 마이크로스펀지 형태의 동결건조 제품으로는 천연고분자인 콜라겐 또는 히아루론산을 매트릭스 성분으로 하는 것이 있는데, 망상결합을 갖지 않는 구조의 콜라겐 스펀지는 동결건조에 의해서 콜라겐 수용액으로부터 제조되거나, 물과 혼합 가능한 유기용매를 이용해 발포시킨 콜라겐 덩어리로부터 물을 제거해 제조되며, 특히 가교구조를 갖는 콜라겐 스펀지는 물에서도 안정한 것으로 알려져 있다(특허문헌 1).The microsponge-type lyophilized products include natural polymers such as collagen or hyaluronic acid as matrix components. Collagen sponges having no network bonds are prepared from collagen aqueous solution by lyophilization or mixed with water. It is manufactured by removing water from the collagen lumps foamed using, and in particular, a collagen sponge having a crosslinked structure is known to be stable in water (Patent Document 1).
또한, 히아루론산 용액에 에폭시계 가교제를 첨가하여 하이드로겔화 시킨 후, 다공성을 부여하기 위하여 팽창시킨 다음, 그 팽창된 히아루론산 하이드로겔을 동결건조 하여 제조한 히아루론산 마이크로스펀지는 기공 크기를 조절할 수 있어 세포배양의 지지체로 응용될 수 있었다(특허문헌 2).In addition, the hyaluronic acid microsponge prepared by adding an epoxy-based crosslinking agent to the hyaluronic acid solution to hydrogel, and then expanded to give porosity, and then lyophilized the expanded hyaluronic acid hydrogel to control the pore size. It could be applied as a support (patent document 2).
그러나 상기 콜라겐 또는 히아루론산 기반의 비가교 마이크로스펀지는 기계적 강도가 떨어지거나, 물과 접촉 시 용해 속도의 조절이 어려운 단점이 있다. 또한, 가교된 마이크로스펀지의 경우에도 기계적 강도의 향상은 기대할 수 있으나, 물에 재용해 되지 않는 성질이 있어 그 응용에 제한이 따른다.However, the collagen or hyaluronic acid-based non-crosslinked microsponge has a disadvantage in that the mechanical strength is poor or it is difficult to control the dissolution rate when contacted with water. In addition, even in the case of cross-linked microsponge can be expected to improve the mechanical strength, there is a property that does not re-dissolve in water, there is a limitation in the application.
한편, 예비동결건조 및 전기기공 제어법에 의하여 기공을 제어함으로써 용해도를 조절하는 방법이 공지되어 있으나, 제조공정이 복잡하고 생산비용의 증가가 수반되어 경제성이 저하되는 문제점이 있다(특허문헌 3). On the other hand, there is a known method of adjusting the solubility by controlling the pores by pre-freeze drying and electroporation control method, but there is a problem that the manufacturing process is complicated and the economic cost is accompanied by an increase in the production cost (Patent Document 3).
따라서 본 발명자는 수용성 천연고분자 또는 합성고분자를 매트릭스 성분으로 하고, 여기에 수용성 또는 수분산성 붕해제를 포함시켜 동결건조된 마이크로스펀지 형태의 성형체를 제조할 수 있으면, 기계적 강도를 유지하는 상태에서 물에 대한 용해도 조절이 가능할 뿐만 아니라, 물과 접촉 시 재용해 특성이 현저히 향상되는 마이크로스펀지를 얻을 수 있음에 착안하여 본 발명을 완성하기에 이르렀다.Therefore, the inventors of the present invention have a water-soluble natural polymer or a synthetic polymer as a matrix component, and if a water-soluble or water-dispersible disintegrant is included therein to form a lyophilized microsponge-shaped molded article, water is kept in water while maintaining mechanical strength. The present invention has been completed by focusing on the fact that not only the solubility can be controlled, but also the microsponge having remarkably improved re-dissolution properties when contacted with water.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
특허문헌 1 한국공개특허공보 제10-2007-0064329호Patent Document 1 Korean Laid-Open Patent Publication No. 10-2007-0064329
특허문헌 2 한국공개특허공보 제10-2007-0108062호Patent Document 2: Korean Patent Publication No. 10-2007-0108062
특허문헌 3 국제공개특허공보 WO 2001/057121Patent Document 3 International Publication WO 2001/057121
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 목적은 용해도 조절이 가능하고, 스펀지의 밀도 및 강도의 조절이 용이하며, 재용해 특성이 우수할 뿐만 아니라, 방부제를 첨가하지 않고서도 장기 보관성 및 유통 안정성을 갖는 마이크로스펀지를 제공하고자 하는 것이다.The present invention has been made in view of the above problems, and an object of the present invention is to control the solubility, to easily control the density and strength of the sponge, not only to excellent re-dissolution characteristics, but also without adding a preservative. It is also to provide a micro sponge having a long-term storage and distribution stability.
상기한 바와 같은 목적을 달성하기 위한 본 발명은, 수용성 고분자 소재; 및 수용성 또는 수분산성 붕해제;를 포함하는 마이크로스펀지를 제공한다.The present invention for achieving the above object is a water-soluble polymer material; And a water-soluble or water-dispersible disintegrant.
상기 수용성 고분자 소재는 베타 글루칸, 히아루론산, 하이드록시프로필메틸 셀룰로오스, 카르복시메틸 셀룰로오스, 하이드록시에틸 셀룰로오스, 키토산, 젤라틴, 폴리비닐알콜, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 폴리아크릴아마이드, 잔탄검, 고분자 콜라겐, 카라기난, 플루란, 펙틴, 콘드로이틴 설페이트, 덱스트란 및 알긴산으로 이루어진 군으로부터 선택된 1종 이상의 것을 특징으로 한다.The water-soluble polymer material is beta glucan, hyaluronic acid, hydroxypropylmethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, chitosan, gelatin, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyacrylamide, xanthan gum, polymer It is characterized by at least one member selected from the group consisting of collagen, carrageenan, pullulan, pectin, chondroitin sulfate, dextran and alginic acid.
상기 수용성 고분자 소재의 함량은 마이크로스펀지에 대하여 0.1 내지 50 중량%인 것을 특징으로 한다.The content of the water-soluble polymer material is characterized in that 0.1 to 50% by weight based on the micro sponge.
상기 수용성 붕해제는 저분자량 카르복시메틸 셀룰로오스, 저분자량 하이드록시프로필메틸 셀룰로오스, 저분자량 하이드록시에틸 셀룰로오스, 저분자량 키틴, 저분자량 키토산, 저분자량 콜라겐, 저분자량 폴리아크릴산, 저분자량 폴리아크릴아마이드, 저분자량 폴리비닐알콜 및 저분자량 폴리에틸렌옥사이드로 이루어진 군으로부터 선택된 1종 이상의 것을 특징으로 한다.The water-soluble disintegrant is a low molecular weight carboxymethyl cellulose, low molecular weight hydroxypropyl methyl cellulose, low molecular weight hydroxyethyl cellulose, low molecular weight chitin, low molecular weight chitosan, low molecular weight collagen, low molecular weight polyacrylic acid, low molecular weight polyacrylamide, low It is characterized by at least one member selected from the group consisting of molecular weight polyvinyl alcohol and low molecular weight polyethylene oxide.
상기 수용성 붕해제는 글루코스, 수크로오스, 말토스 및 락토스로 이루어진 군으로부터 선택된 1종 이상의 것을 특징으로 한다.The water-soluble disintegrant is characterized in that at least one selected from the group consisting of glucose, sucrose, maltose and lactose.
상기 수용성 붕해제는 알파 사이클로덱스트린, 베타 사이클로덱스트린, 감마 사이클로덱스트린, 하이드록시프로필 사이클로덱스트린, 하이드록시에틸 사이클로 덱스트린, 카르복시메틸 사이크로덱스트린, 메틸 사이클로덱스트린 및 글루코실 사이클로덱스트린으로 이루어진 군으로부터 선택된 1종 이상의 것을 특징으로 한다.The water-soluble disintegrant is one selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, hydroxypropyl cyclodextrin, hydroxyethyl cyclodextrin, carboxymethyl cyclodextrin, methyl cyclodextrin and glucosyl cyclodextrin. It is characterized by the above.
상기 수분산성 붕해제는 마이크로콜로이드 실리카, 나노클레이, 티타늄옥사이드, 탈크, 또는 마이카인 무기입자, 또는 아크릴 파우더, 나일론 파우더, 폴리에틸렌 파우더 또는 폴리프로필렌 파우더인 유기입자로부터 선택된 1종 이상의 것을 특징으로 한다.The water dispersible disintegrant is characterized in that at least one selected from microcolloidal silica, nanoclay, titanium oxide, talc, or mica inorganic particles, or organic particles of acrylic powder, nylon powder, polyethylene powder or polypropylene powder.
상기 마이크로스펀지 내에서 수용성 고분자 소재와 수용성 또는 수분산성 붕해제의 중량비는 1 : 0.5 내지 100인 것을 특징으로 한다.The weight ratio of the water-soluble polymer material and the water-soluble or water-dispersible disintegrant in the micro sponge is characterized in that 1: 0.5 to 100.
상기 마이크로스펀지는 기능성 부여 물질을 더욱 포함하는 것을 특징으로 한다.The microsponge is characterized in that it further comprises a functional imparting material.
상기 마이크로스펀지는 계면활성제, 착색제, 착향제, 감미제, 오일, 왁스 및 항산화제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 더욱 포함하는 것을 특징으로 한다.The microsponge is characterized in that it further comprises one or more additives selected from the group consisting of surfactants, colorants, flavors, sweeteners, oils, waxes and antioxidants.
상기 마이크로스펀지는 구형, 하트형, 정제형 또는 시트형으로 제형 가능한 괴상 또는 시트상인 것을 특징으로 한다.The microsponge is characterized in that it is in the form of a sphere or a sheet can be formulated in a spherical, heart-shaped, tablet form or sheet form.
본 발명에 따라 제조된 마이크로스펀지는 용해도 조절이 가능하고, 스펀지의 밀도 및 강도의 조절이 용이하며, 재용해 특성이 우수할 뿐만 아니라, 방부제를 첨가하지 않고서도 장기 보관성 및 유통 안정성이 뛰어나므로, 구형, 하트형, 정제형 또는 시트형으로 제형하여 식품, 의약품, 의약외품, 화장품, 생활용품, 동물약품, 농약 및 공산품 등에 응용이 가능하다.The micro-sponge prepared according to the present invention can control the solubility, control the density and strength of the sponge, not only excellent re-dissolution characteristics, but also excellent long-term storage and distribution stability without adding a preservative. Formulated in spherical, heart, tablet or sheet form, it can be applied to food, medicine, quasi-drugs, cosmetics, household goods, animal drugs, pesticides and industrial products.
도 1은 본 발명에 의한 마이크로스펀지의 제조 및 재용해에 따른 스펀지의 붕괴를 나타낸 모식도.1 is a schematic diagram showing the collapse of the sponge according to the manufacture and re-dissolution of the micro-sponge according to the present invention.
도 2는 본 발명의 실시예 1로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진.Figure 2 is a photograph observing the state of hydration of the microsponge prepared from Example 1 of the present invention.
도 3은 본 발명의 실시예 1로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진.Figure 3 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Example 1 of the present invention.
도 4는 본 발명의 비교예 1로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진.Figure 4 is a photograph observing the state of hydration of the microsponge prepared from Comparative Example 1 of the present invention.
도 5는 본 발명의 비교예 1로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진.Figure 5 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Comparative Example 1 of the present invention.
도 6은 본 발명의 비교예 2로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진.Figure 6 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Comparative Example 2 of the present invention.
도 7은 본 발명의 실시예 3으로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진.Figure 7 is a photograph observing the state of hydration of the microsponge prepared from Example 3 of the present invention.
도 8은 본 발명의 실시예 3으로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진.8 is a scanning electron microscope (SEM) photograph taken of the microsponge prepared from Example 3 of the present invention.
이하에서는 본 발명에 따른 용해도 조절 및 재용해 특성이 향상된 마이크로스펀지에 대하여 상세히 설명하기로 한다.Hereinafter will be described in detail with respect to the improved micro-sponge solubility control and re-dissolution properties according to the present invention.
본 발명은 수용성 고분자 소재; 및 수용성 또는 수분산성 붕해제;를 포함하는 마이크로스펀지를 제공한다.The present invention is a water-soluble polymer material; And a water-soluble or water-dispersible disintegrant.
먼저, 본 발명에서는 마이크로스펀지의 매트릭스 성분으로서 베타 글루칸, 히아루론산, 하이드록시프로필메틸 셀룰로오스, 카르복시메틸 셀룰로오스, 하이드록시에틸 셀룰로오스, 키토산, 젤라틴, 폴리비닐알콜, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 폴리아크릴아마이드, 잔탄검, 고분자 콜라겐, 카라기난, 플루란, 펙틴, 콘드로이틴 설페이트, 덱스트란 및 알긴산으로 이루어진 군으로부터 선택된 1종 이상의 것을 사용하는데, 상기 수용성 고분자 소재는 통상적인 방법으로 실온에서 또는 가열 건조하였을 때, 필름상이나 괴상의 강도를 갖는 고분자량의 것이 바람직하다.First, in the present invention, as a matrix component of the micro sponge, beta glucan, hyaluronic acid, hydroxypropylmethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, chitosan, gelatin, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, and polyacryl Amide, xanthan gum, polymeric collagen, carrageenan, pullulan, pectin, chondroitin sulfate, dextran and alginic acid are used. The water-soluble polymer material is conventionally used at room temperature or when heated to dryness. The thing of the high molecular weight which has film-like or blocky strength is preferable.
또한, 상기 수용성 고분자 소재의 함량은 마이크로스펀지에 대하여 0.1 내지 50 중량%인 것이 바람직하고, 0.2 내지 30 중량%인 것이면 더욱 바람직하다. 이때, 상기 수용성 고분자 소재의 함량이 마이크로스펀지에 대하여 0.1 중량% 미만이면, 매트릭스 성분으로서의 함량이 너무 낮아 마이크로스펀지의 기계적 강도가 떨어질 수 있고, 수용성 고분자 소재의 함량이 마이크로스펀지에 대하여 50 중량%를 초과하면 수용성 또는 수분산성 붕해제의 함량이 상대적으로 낮아져 마이크로스펀지가 물과 접촉 시 재용해성이 저하될 우려가 있다.In addition, the content of the water-soluble polymer material is preferably 0.1 to 50% by weight, and more preferably 0.2 to 30% by weight with respect to the micro sponge. At this time, if the content of the water-soluble polymer material is less than 0.1% by weight with respect to the micro sponge, the content as a matrix component is too low may decrease the mechanical strength of the micro sponge, the content of the water-soluble polymer material is 50% by weight relative to the micro sponge If exceeded, the content of the water-soluble or water-dispersible disintegrant is relatively low, and there is a concern that the re-solubility of the micro sponge is lowered when contacted with water.
또한, 본 발명에서는 마이크로스펀지를 제조하는 과정에서 매트릭스 성분인 수용성 고분자 용액의 점도를 저하시키거나 제조된 마이크로스펀지를 다시 물에 재용해시킬 때, 용해속도를 향상시키는 역할을 하는 것으로 수용성 또는 수분산성 붕해제를 포함하는 것을 기술적 특징으로 한다.In addition, the present invention serves to improve the dissolution rate when reducing the viscosity of the water-soluble polymer solution as a matrix component in the process of manufacturing the micro sponge or redissolved in the water again to the water-soluble or water dispersible It is characterized by including a disintegrant.
상기 수용성 붕해제로서는 저분자량 카르복시메틸 셀룰로오스, 저분자량 하이드록시프로필메틸 셀룰로오스, 저분자량 하이드록시에틸 셀룰로오스, 저분자량 키틴, 저분자량 키토산, 저분자량 콜라겐, 저분자량 폴리아크릴산, 저분자량 폴리아크릴아마이드, 저분자량 폴리비닐알콜 및 저분자량 폴리에틸렌옥사이드로 이루어진 군으로부터 선택된 1종 이상의 것을 사용한다. 한편, 실온에서 또는 가열 건조하였을 때, 섬유상, 펄프상, 분말상 또는 일정한 결정구조를 갖는 고형물 상태로서 물에 대한 용해도 및 용해속도가 높은 것이라면 수용성 고분자라도 무방하다. As the water-soluble disintegrant, low molecular weight carboxymethyl cellulose, low molecular weight hydroxypropylmethyl cellulose, low molecular weight hydroxyethyl cellulose, low molecular weight chitin, low molecular weight chitosan, low molecular weight collagen, low molecular weight polyacrylic acid, low molecular weight polyacrylamide, low molecular weight At least one selected from the group consisting of molecular weight polyvinyl alcohol and low molecular weight polyethylene oxide is used. On the other hand, a water-soluble polymer may be used as long as it has a high solubility in water and a dissolution rate in a fibrous, pulp, powder or solid state having a constant crystal structure at room temperature or when heated to dryness.
또한, 상기 수용성 붕해제로서는 글루코스, 수크로오스, 말토스 및 락토스로 이루어진 군으로부터 선택된 1종 이상의 것으로, 건조 시 분말이거나 결정인 저분자 당류를 사용할 수도 있다.In addition, the water-soluble disintegrant may be one or more selected from the group consisting of glucose, sucrose, maltose and lactose, and may be a low molecular sugar that is powder or crystals upon drying.
또한, 상기 수용성 붕해제로서는 알파 사이클로덱스트린, 베타 사이클로덱스트린, 감마 사이클로덱스트린, 하이드록시프로필 사이클로덱스트린, 하이드록시에틸 사이클로 덱스트린, 메틸 사이클로덱스트린, 카르복시메틸 사이크로덱스트린 및 글루코실 사이클로덱스트린으로 이루어진 군으로부터 선택된 1종 이상의 것으로, 덱스트린계 화합물 또는 그 유도체를 사용할 수도 있다.In addition, the water-soluble disintegrant is selected from the group consisting of alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, hydroxypropyl cyclodextrin, hydroxyethyl cyclodextrin, methyl cyclodextrin, carboxymethyl cyclodextrin and glucosyl cyclodextrin. You may use a dextrin type compound or its derivative (s) with 1 or more types.
한편, 상기 수분산성 붕해제로서는 마이크로콜로이드 실리카, 나노클레이, 티타늄옥사이드, 탈크, 또는 마이카인 무기입자, 또는 아크릴 파우더, 나일론 파우더, 폴리에틸렌 파우더 또는 폴리프로필렌 파우더인 유기입자로부터 선택된 1종 이상의 것을 사용하며, 상기 무기입자 또는 유기입자의 분산성이나 표면특성을 향상시키기 위하여 유기 또는 무기 성분으로 표면 처리된 무기입자 또는 유기입자를 사용하여도 좋다.On the other hand, as the water dispersible disintegrant, at least one selected from microcolloidal silica, nanoclay, titanium oxide, talc, mica inorganic particles or organic particles such as acrylic powder, nylon powder, polyethylene powder or polypropylene powder, In order to improve the dispersibility or surface properties of the inorganic particles or organic particles, inorganic particles or organic particles surface-treated with organic or inorganic components may be used.
상기 수용성 붕해제 또는 수분산성 붕해제는 단독으로 또는 혼합하여 사용할 수 있으되, 상기 마이크로스펀지 내에서 수용성 고분자 소재와 수용성 또는 수분산성 붕해제의 중량비는 1 : 0.5 내지 100인 것이 마이크로스펀지의 용해도와 함께 밀도 및 강도를 쉽게 조절할 수 있고, 물과 접촉 시 재용해 특성을 극대화할 수 있어 바람직하며, 1 : 1 내지 30인 것이면 더욱 바람직하다.The water-soluble disintegrant or water-dispersible disintegrant may be used alone or in combination, but the weight ratio of the water-soluble polymer material and the water-soluble or water-dispersible disintegrant in the micro sponge is 1: 0.5 to 100 with the solubility of the micro sponge. Density and strength can be easily adjusted, it is preferable to maximize the re-dissolution properties when in contact with water, and more preferably 1: 1 to 30.
이때, 사이클로덱스트린과 그 유도체, 그리고 다공성 실리카와 같은 유기 또는 무기 화합물 처리 다공성 비드류는 물에 분산 또는 용해시키기 전에 저분자의 기능성 부여 물질을 사전에 침지, 포집해 이를 물에 분산 및 용해시킴으로써 사용 전에 마이크로스펀지가 물에 붕해되어 재용해 되었을때, 침지 포집되어 있는 기능성부여 물질을 서서히 방출함으로써 그 효능을 나타낼 수 있으며, 이러한 서방성 기능은 화장품, 의약품, 소취, 방향제를 포함한 생활용품, 농약 및 비료 등의 공산품 등에 광범위하게 사용될 수 있다.At this time, cyclodextrin and its derivatives, and organic or inorganic compound-treated porous beads such as porous silica, before dispersing or dissolving in water, before immersing, collecting and dispersing and dissolving the low molecular weight imparting substance in water before use When the microsponge disintegrates in water and re-dissolves, it can show its efficacy by slowly releasing the impregnated functional impregnated substances, and these sustained-release functions are cosmetics, medicines, deodorants, household goods including fragrances, pesticides and fertilizers. It can be widely used for industrial products, such as these.
따라서 본 발명에서는 마이크로스펀지에 기능성 부여 물질을 더욱 포함할 수 있는바, 상기 기능성 부여 물질로서는 재용해 되었을 때, 방출되어 기능을 나타내는미백제, 항발적제, 자외선차단제, 보습제, 습윤제, 박리제, 항노화제, 항주름제, 체중감량제, 체중증가제, 탄성을 개선시키는 성분, 교질(collagen) 또는 엘라스틴 합성을 자극하는 성분, 항여드름제, 항염증제, 항산화제, 항자유라디칼 성분, 프로착색제 또는 탈색소제, 펩티드, 비타민 또는 그 유도체,향 정유, 항바이러스제, 항진균제, 진통소염제, 항알레르기제, 발기부전 치료제, 해열 진통제, 위장약, 비만치료제, 다이어트용 보조제, 식이섬유류, 필수 미네랄, 토코페롤 유도체, 필수 단백질 및 아미노산 등을 포함해 외용, 구강내용, 복용이 가능한 의약품, 화장품 또는 건강보조식품 성분들 중에서 선택된 1종 이상을 포함하지만, 이들에 국한되지는 않는다.Therefore, the present invention may further include a functional imparting substance in the microsponge, wherein the functional imparting substance, when redissolved, is released and exhibits a function, a whitening agent, an anti-depressant agent, a sunscreen agent, a moisturizer, a humectant, a release agent, and an anti-aging agent. Agents, anti-wrinkle agents, weight loss agents, weight gain agents, ingredients that improve elasticity, ingredients that stimulate collagen or elastin synthesis, anti acne agents, anti-inflammatory agents, antioxidants, anti-free radical ingredients, pro-colorants, or bleaching Antiseptic, antiviral, antifungal, analgesic, antiallergic, erectile dysfunction, antipyretic analgesic, gastrointestinal, anti-obesity, dietary supplement, dietary fiber, essential minerals, tocopherol derivatives, essential Among the ingredients for medicines, cosmetics or dietary supplements that can be taken externally, oral, and taken, including proteins and amino acids These include at least one standing, but are not limited to these.
상기 기능성 부여물질의 성상은 수용성, 난용성, 유용성 또는 수분산성의 것으로서 오일상 또는 왁스상이어도 좋다.The properties of the functional imparting substance are water-soluble, poorly soluble, oil-soluble, or water-dispersible, and may be oil or waxy.
특히, 오일상 또는 왁스상 기능성 부여물질을 함유시키기 위해서는 마이크로 캡슐화 또는 유화 등의 기존 방법을 사용하지 않고, 매트릭스 성분과 붕해제의 수용액에 분산시켜 동결시킨 후, 이를 동결건조함으로써 오일상 또는 왁스상의 기능성 부여물질이 스펀지의 공극에 안정하게 포접된 마이크로스펀지가 얻어진다.In particular, in order to contain an oil- or wax-like functional imparting substance, without using a conventional method such as micro-encapsulation or emulsification, it is dispersed in an aqueous solution of the matrix component and the disintegrant and frozen, and then lyophilized to obtain an oil- or wax-like phase. A microsponge having a functional imparting substance stably included in the pores of the sponge is obtained.
한편, 본 발명에 따른 마이크로스펀지는 방부제를 첨가하지 않고서도 장기 보관성 및 유통 안정성을 갖는 것을 하나의 기술적 특징으로 하지만, 필요에 따라서는 방부제와 같은 보존제, 또는 색, 향, 및 맛을 느낄 수 있는 물질을 첨가할 수도 있는바, 본 발명에서는 마이크로스펀지에 계면활성제, 착색제, 착향제, 감미제, 항산화제 및 보존제로 이루어진 군으로부터 선택된 1종 이상의 첨가제가 더욱 포함됨으로써 마이크로스펀지의 재용해 시 물리적 특성이 부여된다.On the other hand, although the microsponge according to the present invention has one technical feature of having long-term storage and distribution stability without adding a preservative, it is possible to feel a preservative such as a preservative, or color, aroma, and taste as necessary. In the present invention, the micro sponge may further include at least one additive selected from the group consisting of a surfactant, a colorant, a flavoring agent, a sweetener, an antioxidant, and a preservative, so that the physical properties of the microsponge during re-dissolution are further included. Is given.
상기 마이크로스펀지는 동결건조 후의 형태가 동결건조 과정에서 사용되는 용기의 디자인과 원료물질의 특성에 따라서 수축이나 팽창할 수 있고, 표면특성 및 색상이 변화될 수 있으며, 구형, 하트형, 정제형 또는 시트형으로 제형 가능한 괴상 또는 시트상으로 얻어진다.The microsponge may shrink or expand according to the design of the container used in the freeze-drying process and the characteristics of the raw material after freeze-drying, surface properties and colors may be changed, and the spherical, heart-shaped, tablet-type or It is obtained in the form of a sheet or a sheet which can be formulated in a sheet form.
한편, 본 발명에 따른 마이크로스펀지는 표면층뿐만 아니라 단면도 일정한 형태의 기공을 형성하고 있으며, 매트릭스 성분인 수용성 고분자 소재와 수용성 또는 수분산성 붕해제가 균일하게 하나의 물질처럼 스펀지 형태로 존재하고 있음을 주사전자현미경(SEM)으로 확인하였다. 게다가 물에 수화되었을 때, 물이 모세관 현상에 의하여 기공으로 급속하게 유입되면서 물에 빠르게 용해되거나 분산되는 붕해제가 먼저 급속하게 용해되거나 분산되면서 물의 내부 침투를 훨씬 빠르게 유도하는 효과가 있으며, 내부까지 도달한 충분한 양의 물에 다시 매트릭스 성분인 수용성 고분자 소재가 계속해서 수화 용해됨으로서 매우 빠른 속도로 붕괴/용해됨을 확인할 수 있었다. 반면, 종래 수용성 고형제만으로 제조된 마이크로스펀지 상의 성형체도 유사한 구조를 가지고 있으나, 수용성 고형제만으로 이루어진 마이크로스펀지의 경우, 초기에는 본 발명의 마이크로스펀지에서와 같이 모세관 현상에 의하여 기공으로 물이 빠르게 유입되지만, 바깥쪽 부분의 수용성 고형제가 수화되어 용해되면서 점도가 급속도로 상승하여 더 이상의 물이 내부로 유입되거나 전달되는 것을 막게 되어 내부의 수용성 고형제가 물에 수화되어 완전히 녹기 까지는 많은 시간이 소요되고, 문지르거나 저어주고 또는 용기를 흔들어서 물리적인 힘으로 다시 물에 수화 시켜 용해시키지 않으면 완전히 녹이기 어려운 단점이 있다.Meanwhile, the microsponge according to the present invention forms pores with a uniform cross-sectional shape as well as the surface layer, and scans that the water-soluble polymer material, which is a matrix component, and the water-soluble or water-dispersible disintegrant, are uniformly present in the form of a sponge as one material. It was confirmed by an electron microscope (SEM). Furthermore, when hydrated in water, disintegrants, which dissolve or disperse rapidly in water as they rapidly enter the pores by capillary action, first dissolve or disperse rapidly and induce the internal penetration of water much faster. It was confirmed that the water-soluble polymer material, which is a matrix component, was continuously hydrated and dissolved in a sufficient amount of water so as to disintegrate / dissolve at a very high rate. On the other hand, the molded article on the micro-sponge prepared by the conventional water-soluble solid agent has a similar structure, but in the case of the micro sponge made of only the water-soluble solid agent, water is rapidly introduced into the pores by capillary action as in the micro sponge of the present invention. However, as the water-soluble solid agent in the outer portion is hydrated and dissolved, the viscosity rises rapidly to prevent further water from flowing into or transferred to the water-soluble solid agent, which takes a long time until the water-soluble solid agent is hydrated in water and completely dissolved. If you do not dissolve by rubbing or stirring or shaking the container by hydrating the water again with physical force, it is difficult to dissolve completely.
이하에서는 본 발명에 따른 실시예 및 비교예를 첨부된 도면과 함께 구체적으로 서술한다. 도 1에는 본 발명에 의한 마이크로스펀지의 제조 및 재용해에 따른 스펀지의 붕괴를 나타낸 모식도를 나타내었다.Hereinafter, embodiments and comparative examples according to the present invention will be described in detail with the accompanying drawings. Figure 1 shows a schematic diagram showing the collapse of the sponge according to the manufacture and re-dissolution of the micro-sponge according to the present invention.
[실시예 1] 수용성 붕해제를 포함하는 마이크로스펀지 제조 1Example 1 Preparation of Microsponge Containing a Water-soluble Disintegrant
수용성 고분자 소재인 베타 글루칸 수용액(0.5 중량%) 100g에, 수용성 붕해제인 마린 콜라겐(저분자량 콜라겐) 3g과 수용성 올리고 키토산(저분자량 키토산) 5g을 첨가 및 실온에서 용해시켜 혼합용액을 얻었다. 이어서 상기 혼합용액을 직경이 11mm인 구형의 틀에 넣어 저온 냉동고에 넣고 -40℃에서 1시간 동안 동결한다. 마지막으로, 동결된 볼을 틀에서 분리해 노출된 상태에서 동결건조기에 넣어 24시간 동안 건조함으로써 마이크로스펀지를 제조하였다.To 100 g of aqueous solution of beta glucan (0.5 wt%), which is a water-soluble polymer, 3 g of marine collagen (low molecular weight collagen), which is a water-soluble disintegrant, and 5 g of water-soluble oligo chitosan (low molecular weight chitosan) were added and dissolved at room temperature to obtain a mixed solution. Subsequently, the mixed solution was placed in a spherical mold having a diameter of 11 mm, placed in a low temperature freezer, and frozen at -40 ° C. for 1 hour. Finally, the frozen balls were removed from the mold and placed in a freeze dryer in an exposed state to dry for 24 hours to prepare a microsponge.
[실시예 2] 수용성 붕해제를 포함하는 마이크로스펀지 제조 2Example 2 Preparation of Microsponge 2 Containing Water Soluble Disintegrant
베타 글루칸 수용액(1 중량%) 30g 및 히아루론산 나트륨 수용액(0.5 중량%) 70g에, 베타 사이클로덱스트린 2g 및 마린 콜라겐 2g을 사용하여 혼합용액을 얻은 것을 제외하고는 실시예 1과 동일한 방법으로 마이크로스펀지를 제조하였다.Microsponge was prepared in the same manner as in Example 1, except that 30 g of aqueous solution of beta glucan (1% by weight) and 70 g of aqueous solution of sodium hyaluronate (0.5% by weight) were used to obtain a mixed solution using 2 g of beta cyclodextrin and 2 g of marine collagen. Prepared.
[실시예 3] 기능성 부여물질을 포함하는 마이크로스펀지 제조Example 3 Preparation of Microsponge Containing Functional Imparting Material
베타 글루칸 수용액(1 중량%) 20g과 히아루론산 나트륨 수용액(0.5 중량%) 80g을 혼합 및 교반하여 혼합용액을 얻었다. 한편으로, 하이드록시프로필 사이클로덱스트린 2g 및 마린 콜라겐 2g 파우더 혼합물을 준비하고, 로즈힙 오일 1g과 토코페롤 1g의 오일 혼합물에 시어버터 0.5g을 첨가하여 70℃에서 시어버터를 용해시켰다. 이어서 상기 오일 혼합물을 하이드록시프로필 사이클로덱스트린과 마린 콜라겐 파우더 혼합물에 부어 반죽과 같이 만들고, 이를 베타 글루칸 수용액과 히아루론산 나트륨 수용액의 혼합용액에 다시 분산시켰다. 상기 분산용액으로부터 실시예 1과 동일한 방법으로 마이크로스펀지를 제조하였다.20 g of aqueous beta glucan solution (1 wt%) and 80 g of aqueous sodium hyaluronate solution (0.5 wt%) were mixed and stirred to obtain a mixed solution. Meanwhile, 2 g of hydroxypropyl cyclodextrin and 2 g of marine collagen powder mixture were prepared, and 0.5 g of shea butter was added to an oil mixture of 1 g of rosehip oil and 1 g of tocopherol to dissolve the shea butter at 70 ° C. The oil mixture was then poured into a mixture of hydroxypropyl cyclodextrin and marine collagen powder to form a dough, which was then dispersed again in a mixed solution of aqueous beta glucan solution and aqueous sodium hyaluronate solution. A microsponge was prepared from the dispersion solution in the same manner as in Example 1.
[실시예 4] 기능성 부여물질 및 첨가제를 포함하는 마이크로스펀지 제조Example 4 Preparation of Microsponge Containing Functional Imparting Substance and Additive
베타 글루칸 수용액(0.5 중량%) 30g과 히아루론산 나트륨 수용액(0.5 중량%) 70g을 혼합 및 교반하고, 여기에 마린 콜라겐 1g 및 나일론 파우더 1g을 용해시켜 혼합용액을 얻고 저온(4℃)에서 방치한다. 한편으로, 알파 사이클로덱스트린 12g에 로즈힙 오일 3g, 토코페롤 0.5g을 흡수 및 이를 상기 혼합용액에 다시 용해, 분산시킨 다음, 붉은 색을 띄는 홍국 추출물을 함께 용해시킨 후, 이로부터 실시예 1과 동일한 방법으로 마이크로스펀지를 제조하였다.30 g of aqueous solution of beta glucan (0.5% by weight) and 70g of aqueous solution of sodium hyaluronate (0.5% by weight) are mixed and stirred, and 1 g of marine collagen and 1 g of nylon powder are dissolved to obtain a mixed solution and left at low temperature (4 ° C). Meanwhile, 3 g of rose hip oil and 0.5 g of tocopherol were absorbed in 12 g of alpha cyclodextrin and dissolved in the mixed solution, and then dispersed, and then, the red color red yeast extract was dissolved together, and then the same method as in Example 1 Microsponge was prepared.
[비교예 1] 수용성 붕해제를 포함하지 않는 마이크로스펀지 제조 1[Comparative Example 1] Preparation of a micro sponge containing no water-soluble disintegrant 1
물 100g에 히아루론산 나트륨 1g을 용해시킨 히아루론산 나트륨 수용액만으로부터 실시예 1과 동일한 방법으로 마이크로스펀지를 제조하였다.A microsponge was prepared in the same manner as in Example 1 only from an aqueous sodium hyaluronate solution in which 1 g of sodium hyaluronate was dissolved in 100 g of water.
[비교예 2] 수용성 붕해제를 포함하지 않는 마이크로스펀지 제조 2[Comparative Example 2] Preparation of micro sponge 2 containing no water-soluble disintegrant
물 100g에 베타 글루칸 1g을 용해시킨 베타 글루칸 수용액만으로부터 실시예 1과 동일한 방법으로 마이크로스펀지를 제조하였다.Microsponge was prepared in the same manner as in Example 1 only from beta glucan aqueous solution in which 1 g of beta glucan was dissolved in 100 g of water.
도 2에는 본 발명의 실시예 1로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진을 나타내었는바, 도 2에서 보는 바와 같이, 제조된 볼 형태의 마이크로스펀지를 물에 떨어뜨린 후에 시간이 경과함에 따라 외력이 가해지지 않아도 동결건조해서 형성된 기공으로 물이 모세관 현상에 의해 빠르게 유입됨과 동시에 붕해제(붕괴제)가 녹으면서 마이크로스펀지가 빠른 속도로 붕괴되면서 녹는 것을 알 수 있다.Figure 2 shows a photograph observing the hydration state of the micro-sponge prepared from Example 1 of the present invention, as shown in Figure 2, time after dropping the prepared ball-type microsponge in water Therefore, even though no external force is applied, the pores formed by lyophilization are rapidly introduced into the pores by capillary action, and at the same time, the disintegrant (disintegrant) melts and the microsponge disintegrates rapidly.
또한, 도 3에는 본 발명의 실시예 1로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진을 나타내었는바, 수용성 고분자 소재와 수용성 붕해제가 서로 상분리 되지 않고 균일하게 셀의 벽을 형성하고 있으며, 또한 규칙적인 셀의 공극이 형성되어 있음을 확인할 수 있다.3 shows a scanning electron microscope (SEM) photograph of the microsponge prepared in Example 1 of the present invention, wherein the water-soluble polymer material and the water-soluble disintegrant do not phase separate from each other to form a uniform wall of the cell. In addition, it can be confirmed that the gap of the regular cells is formed.
한편, 도 4에는 본 발명의 비교예 1로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진을 나타내었는바, 도 4에서 보는 바와 같이, 제조된 볼 형태의 마이크로스펀지를 물에 떨어뜨린 후에 시간이 경과함에 따라 초기에는 어느 정도 외부가 수화되어 용해되나, 시간이 경과할수록 수화 속도가 느려져 결국에는 외부에서 물리적인 외력이 가해지지 않으면 완전히 녹이는데 상당한 시간이 소요되는 것을 확인할 수 있다.On the other hand, Figure 4 shows a photograph observing the state of hydration of the microsponge prepared from Comparative Example 1 of the present invention, as shown in Figure 4, the time after dropping the prepared ball-shaped microsponge in water As the elapsed time, the outside is hydrated and dissolved to some extent, but as time passes, the hydration rate is slowed down, and eventually, it takes a considerable time to completely dissolve unless physical external force is applied from the outside.
또한, 도 5 및 6에는 각각 본 발명의 비교예 1 및 2로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진을 나타내었는바, 비교예 1로부터 제조된 마이크로스펀지는 상대적으로 균일한 셀 구조를 갖는 것을 알 수 있으나, 비교예 2로부터 제조된 마이크로스펀지의 경우에는 공극의 형성은 잘 이루어진 반면, 셀 벽이 지나치게 얇고 성긴 구조를 가짐으로써 수화는 잘 되나, 취급할 수 없을 정도로 취약한 구조를 가지고 있음을 확인할 수 있다.5 and 6 show scanning electron microscope (SEM) images of microsponges prepared from Comparative Examples 1 and 2 of the present invention, respectively. The microsponges prepared from Comparative Example 1 were relatively uniform cells. It can be seen that it has a structure, but in the case of the microsponge manufactured from Comparative Example 2, the pores are well formed, while the cell wall has an excessively thin and coarse structure to hydrate well, but the structure is fragile enough to handle. You can check that you have it.
또한, 도 7에는 본 발명의 실시예 3으로부터 제조된 마이크로스펀지의 수화되는 상태를 관찰한 사진을 나타내었는바, 실시예 1로부터 제조된 마이크로스펀지에는 포함되지 않은 기능성 부여 물질로서 오일 성분의 함량이 높아, 스펀지의 공극에 오일이 분산되어 있는 구조임에도 불구하고, 수용성 붕해제로 사용된 하이드록시프로필 사이클로덱스트린과 저분자량 마린 콜라겐의 수화가 빠르게 진행됨으로써 실시예 1과 거의 유사한 속도로 붕괴되는 것을 확인할 수 있다. 따라서 수용성 붕해제가 스폰지를 물에 재용해시키는데 중요한 역할을 한다는 것을 거듭 알 수 있다.In addition, Figure 7 shows a photograph observing the hydration state of the microsponge prepared from Example 3 of the present invention, the content of the oil component as a functional imparting substance not included in the microsponge prepared from Example 1 High, despite the structure of the oil dispersed in the pores of the sponge, hydroxypropyl cyclodextrin used as a water-soluble disintegrant and low-molecular weight of marine collagen was rapidly hydrated to confirm that it collapses at almost the same rate as in Example 1 Can be. Therefore, it can be seen again that water-soluble disintegrants play an important role in re-dissolving the sponge in water.
또한, 도 8에는 본 발명의 실시예 3으로부터 제조된 마이크로스펀지를 촬영한 주사전자현미경(SEM) 사진을 나타내었는바, 균일하게 형성된 공극의 내부에 물에 용해되지 않는 오일 성분이 균일하게 분산되어 있는 것을 확인할 수 있다.8 shows a scanning electron microscope (SEM) photograph of the microsponge prepared in Example 3 of the present invention, in which oil components which are not dissolved in water are uniformly dispersed in the uniformly formed pores. I can confirm that there is.
또한, 아래 표 1에는 상기 실시예 1 내지 4 및 비교예 1, 2로부터 제조된 마이크로스펀지의 수화용액별 재용해 시간 및 그의 피부 도포시 사용감을 나타내었다.In addition, Table 1 below shows the re-dissolution time for each hydration solution of the microsponges prepared from Examples 1 to 4 and Comparative Examples 1 and 2, and the feeling of use when applying the skin thereof.
표 1
1) 미용액 조성: 부틸렌글라이콜 10부, 글리세린 3부, 피이지/피피지-17/6코폴리머 0.3부, 피이지-75 0.2부, 잔탄검 1부, 피이지-60 하이드로제네이티드캐스터오일 0.3부, 디소듐이디티에이 0.1부, 소듐하이알루로네이트 1부, 캐모마일꽃/잎추출물 3부, 세이지추출물 0.5부, 라벤더추출물 0.5부, 로즈마리잎추출물 3부, 페녹시에탄올 0.8부, 향료 0.3부 및 정제수 76부 1) Cosmetic composition: 10 parts butylene glycol, 3 parts glycerin, 0.3 parts sebum / fiji-17 / 6 copolymer, 0.2 parts sebum-75 0.2 parts, xanthan gum, 1 part sebum-60 hydrogenated caster 0.3 parts of oil, 0.1 parts of disodium ethane, 1 part of sodium hyaluronate, 3 parts of chamomile flower / leaf extract, 0.5 parts of sage extract, 0.5 parts of lavender extract, 3 parts of rosemary leaf extract, 0.8 parts of phenoxyethanol, 0.3 parts of fragrances and 76 parts of purified water
2) 취급할 수 없을 정도로 취약하여 원활한 피부 도포 불가 2) It is not vulnerable to handling, so it is impossible to apply skin smoothly.
상기 표 1에서 보는 바와 같이, 본 발명의 실시예 1 내지 4로부터 제조된 마이크로스펀지는 비교예 1로부터 제조된 마이크로스펀지에 비하여 수화용액이 물 또는 미용액이어도 재용해 시간이 현저하게 짧고(비교예 2는 취급할 수 없을 정도로 취약한 구조를 가져 피부 도포를 포함한 적용이 불가하므로 재용해 시간에 의미가 없음), 피부도포시 사용감도 우수함을 알 수 있다. 아울러 본 발명으로부터 제조되는 마이크로스펀지는 통상의 방부제가 전혀 포함되지 않은 상태에서도 장기 보관성 및 유통 안정성이 뛰어난 것으로 확인되었다. As shown in Table 1, the microsponge prepared from Examples 1 to 4 of the present invention is significantly shorter re-dissolution time, even if the hydration solution is water or cosmetics compared to the micro sponge prepared in Comparative Example 1 (Comparative Example 2 It has a fragile structure that cannot be handled, so it is not applicable to skin dissolution time because it is not applicable), and it can be seen that it has excellent feeling when applying skin. In addition, the microsponge produced from the present invention was confirmed to be excellent in long-term storage and distribution stability even when no conventional preservatives are included.
그러므로 본 발명에 따라 제조된 마이크로스펀지는 용해도 조절이 가능하고, 스펀지의 밀도 및 강도의 조절이 용이하며, 재용해 특성이 우수할 뿐만 아니라, 방부제를 첨가하지 않고서도 장기 보관성 및 유통 안정성이 뛰어나므로, 구형, 하트형, 정제형 또는 시트형으로 제형하여 식품, 의약품, 의약외품, 화장품, 생활용품, 동물약품, 농약 및 공산품 등에 응용이 가능하다.Therefore, the micro-sponge prepared according to the present invention can control the solubility, easy to control the density and strength of the sponge, excellent re-dissolution properties, excellent long-term storage and distribution stability without addition of preservatives Therefore, it is possible to apply to food, pharmaceuticals, quasi-drugs, cosmetics, household goods, animal medicines, pesticides and industrial products in the form of sphere, heart, tablet or sheet.
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| KR20160131487A (en) * | 2015-05-07 | 2016-11-16 | 주식회사 블리스팩 | Microsponges having controlled solubility and improved redissolution property |
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2016
- 2016-08-18 WO PCT/KR2016/009093 patent/WO2018034364A1/en not_active Ceased
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|---|---|---|---|---|
| KR20020086485A (en) * | 2000-02-03 | 2002-11-18 | 가부시끼가이샤 메니콘 | Spongy molding comprising water-soluble polymeric material and method of controlling pores thereof |
| KR100996106B1 (en) * | 2002-09-05 | 2010-11-22 | 킴벌리-클라크 월드와이드, 인크. | Extrusion cleaning products |
| KR20070108062A (en) * | 2006-05-04 | 2007-11-08 | 재단법인서울대학교산학협력재단 | Method for preparing porous hyaluronic acid sponge for cell delivery system |
| KR20070064329A (en) * | 2007-03-23 | 2007-06-20 | 군제 가부시키가이샤 | Method for producing collagen sponge, method for manufacturing artificial skin, substrate for artificial skin and cell tissue culture |
| KR20160131487A (en) * | 2015-05-07 | 2016-11-16 | 주식회사 블리스팩 | Microsponges having controlled solubility and improved redissolution property |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112043678A (en) * | 2020-09-18 | 2020-12-08 | 福州爱建生物科技有限公司 | Oral cavity peculiar smell self-receptor |
| CN114632434A (en) * | 2022-03-21 | 2022-06-17 | 哈尔滨工业大学 | Nano SiO2Process for preparing powder-sugar solution |
| CN114632434B (en) * | 2022-03-21 | 2023-01-24 | 哈尔滨工业大学 | Nano SiO 2 Method for preparing powder-sugar solution |
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