KR20160101374A - Nanofiber sheet and manufacturing method thereof - Google Patents
Nanofiber sheet and manufacturing method thereof Download PDFInfo
- Publication number
- KR20160101374A KR20160101374A KR1020150023814A KR20150023814A KR20160101374A KR 20160101374 A KR20160101374 A KR 20160101374A KR 1020150023814 A KR1020150023814 A KR 1020150023814A KR 20150023814 A KR20150023814 A KR 20150023814A KR 20160101374 A KR20160101374 A KR 20160101374A
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- South Korea
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- nanofiber
- nanofiber sheet
- functional group
- polysaccharide polymer
- sheet according
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D44/00—Other cosmetic or toiletry articles, e.g. for hairdressers' rooms
- A45D44/002—Masks for cosmetic treatment of the face
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D44/00—Other cosmetic or toiletry articles, e.g. for hairdressers' rooms
- A45D44/22—Face shaping devices, e.g. chin straps; Wrinkle removers, e.g. stretching the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0212—Face masks
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
Abstract
The present invention relates to a nanofiber sheet comprising a complex of a polysaccharide polymer having an anionic functional group, a complex of a polysaccharide polymer having a cationic functional group and a nanofiber layer composed of a water-soluble polymer, and applying the nanofiber sheet as a mask pack for skin care Technology.
Since the nanofiber sheet prepared according to the present invention has excellent biocompatibility and improved skin adhesion and the nanofiber layer has a crosslinked structure in the form of an acid-base complex, the nanofiber layer can not be peeled off even after the formation of the nanofiber sheet, It has an effect that it can be maintained for a long time.
Description
The present invention relates to a nanofiber sheet and a method for producing the nanofiber sheet. More particularly, the present invention relates to a nanofiber sheet comprising a nanofiber layer comprising a polysaccharide polymer having an anionic functional group, a complex of a polysaccharide polymer having a cationic functional group, To a technique for manufacturing a sheet and applying it to a mask pack or the like for skin beauty.
Recently, there has been a lot of interest in skin care, especially for women, and various methods for skin care have been proposed. Among them, mask packs are relatively easy to use than skin care methods such as laser treatment As the demand grows, the related market is also continuing to grow.
Such mask packs for skin beauty are produced in various forms such as cellulose sheet, hydrogel, velvet and rubber pack, and are entering the market. In particular, in the case of a cellulose sheet, it is easy to apply a natural substance having various functions or an extract thereof in the form of an essence because of its advantage of good water absorbency and harmlessness as a natural substance. However, the cellulose sheet usually has a nonwoven- The surface is rough and the adsorption and absorption rate are lowered. As a result, the adhesion between the sheet and the surface of the skin is deteriorated and the sheet is lifted.
In order to solve the above-described problems, there has been known a technique in which a metal foil is attached to a cellulose sheet and then a voltage or an electric current is supplied to permeate the physiologically active substance impregnated into the mask, And it is also possible to cause stability problems such as electric shock because the electric current is flowed in use (Patent Document 1).
On the other hand, there is known a mask pack in which the skin adhesion is enhanced by forming a mask sheet in which nanofibers having a very small fiber diameter and nonwoven fabric supporting thereon are complexed. However, the mask pack has a weak adhesive force between the nonwoven fabric and the nanofibers Since the organic solvent which is harmful to the skin is used when the nanofiber layer composed of the bilayer structure is used, a person with sensitive skin may have side effects such as allergic reaction (Patent Document 2).
In addition, in order to overcome the disadvantage that the biocompatibility is poor when a mask pack is manufactured using a synthetic polymer as a main material, a method of manufacturing a sponge using a natural polymer such as hyaluronic acid as a main material is known, and a chemical crosslinking agent such as divinylsulfonic acid So that the hyaluronic acid can form a crosslinked structure, and the hyaluronic acid, which is soluble in water, can be insolubilized to maintain its shape even after drying. However, when a chemical crosslinking agent such as divinylsulfone is used, unreacted crosslinking agent remains in the human body Toxicity can be caused, thereby limiting the use (Patent Document 3).
Therefore, the inventors of the present invention have conducted extensive research to develop a mask pack product. As a result, the present inventors have found that when a polysaccharide polymer solution having an anionic functional group and a polysaccharide polymer solution having a cationic functional group are electrospun together on one collector plate, It is possible to manufacture a nanofiber sheet including a nanofiber layer having a cross-linked structure, and it is possible to solve the problem that biocompatibility or skin adhesion force is low when a conventional synthetic polymer or a cellulose sheet is used as a mask pack, Since the nanofiber layer is not peeled off and the moisture resistance can be maintained for a long time by forming the crosslinked structure without using the nanofiber sheet, the nanofiber sheet produced by the present invention can be applied as a mask pack for skin care. .
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a nanocomposite sheet, which has excellent biocompatibility and improves skin adhesion, and which can maintain moisture resistance for a long time, To provide a nanofiber sheet having a crosslinked structure in the form of a base complex and a method for producing the same.
In order to accomplish the above object, the present invention provides a method for producing a nanoparticle comprising (a) a complex of a polysaccharide polymer having an anionic functional group and a polysaccharide polymer having a cationic functional group, and (b) A nanofiber sheet is provided.
The polysaccharide polymer having anionic functional groups may be selected from the group consisting of alginic acid or a salt thereof, hyaluronic acid or a salt thereof, a pectic acid or a salt thereof, polyglucuronic acid or a salt thereof, pectin, heparin, Xanthan gum, chondroitin sulfate, dermatan sulfate, dextran sulfate, and mixtures thereof.
Wherein the alginate is any one selected from the group consisting of sodium alginate, propylene glycol alginate, propylene glycol alginate ester, ammonium alginate, and mixtures thereof.
The polysaccharide-based polymer having a cationic functional group is chitosan or a derivative thereof.
The chitosan or a derivative thereof is characterized by having a deacetylation degree of 75 to 100%.
The water-soluble polymer is any one selected from the group consisting of polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, and mixtures thereof.
Wherein the nanofiber layer comprises (a) 20 to 99% by weight of a complex of a polysaccharide polymer having an anionic functional group and a polysaccharide polymer having a cationic functional group, and (b) 1 to 80% by weight of a water soluble polymer .
Wherein the nanofiber sheet further comprises a functional cosmetic ingredient.
The functional cosmetic ingredient is characterized by any one selected from the group consisting of a moisturizer, a whitening agent, a wrinkle-reducing agent, an antioxidant, and a mixture thereof.
The nanofibers have an average diameter of 10 to 1,000 nm.
The nanofiber sheet has a thickness of 0.05 to 1,000 mu m.
The present invention also provides a mask pack comprising the nanofiber sheet.
The present invention also provides a method for preparing a spinning solution 1, comprising: I) obtaining a spinning solution 1 in which a polysaccharide polymer having an anionic functional group and a water-soluble polymer are mixed; II) obtaining a spinning solution 2 in which a polysaccharide polymer having a cationic functional group and a water-soluble polymer are mixed; And III) supplying and discharging the spinning solutions 1 and 2 to respective spinning nozzles and electrospinning the spinning solution onto one collector plate to form a nanofiber layer.
Characterized in that the electrospinning is carried out at 20 to 40% relative humidity.
Characterized in that the electrospinning is carried out at a voltage of 10 to 30 kv.
The electrospinning is characterized in that the spinning liquids 1 and 2 have a discharge speed of 0.1 to 10 ml / hr.
Since the nanofiber sheet prepared according to the present invention has excellent biocompatibility and improved skin adhesion and the nanofiber layer has a crosslinked structure in the form of an acid-base complex, the nanofiber layer can not be peeled off even after the formation of the nanofiber sheet, It has an effect that it can be maintained for a long time.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view showing contact areas according to respective fiber structures in order to compare nanofibers with microfibers; FIG.
Fig. 2 is a diagram showing the electrospinning process according to the present invention. Fig.
FIG. 3 is a photograph of a nanofiber formed by electrospinning with a high-speed camera according to an embodiment of the present invention. FIG.
4 is a scanning electron microscope (SEM) photograph of a surface of a nanofiber formed by electrospinning according to an embodiment of the present invention.
Hereinafter, a nanofiber sheet according to the present invention, a mask pack including the same, and a method of manufacturing the same will be described in detail.
First, the present invention provides a nanofiber sheet comprising (a) a complex of a polysaccharide polymer having an anionic functional group and a polysaccharide polymer having a cationic functional group, and (b) a nanofiber layer composed of a water-soluble polymer.
The nanofiber layer of the present invention has a network crosslinked structure without using a conventional chemical crosslinking agent which is harmful to the human body so that even if it comes in contact with water, it can not dissolve in water and maintain an long- As a material for forming an acid-base complex, there is used a polysaccharide polymer having an anionic functional group excellent in biocompatibility and a polysaccharide polymer having a cationic functional group, respectively.
The polysaccharide polymer having anionic functional groups may be selected from the group consisting of alginic acid or a salt thereof, hyaluronic acid or a salt thereof, a pectic acid or a salt thereof, polyglucuronic acid or a salt thereof, pectin, heparin, Xanthan gum, chondroitin sulfate, dermatan sulfate, dextran sulfate, and mixtures thereof. Particularly, alginic acid is an anionic natural polymer having a carboxyl group in the molecular chain, which is extracted from brown algae such as sea tangle, seaweed, and kim. It is known that alginic acid exhibits excellent effects in moisturizing, As the polysaccharide-based polymer having anionic functional groups, alginic acid or a salt thereof is more preferably used.
In addition, in the case of the above-mentioned alginate, a variety of derivatives including metal salts of alginic acid in which a carboxyl group of alginic acid is substituted with a metal may be used without limitation, but it is preferable to use sodium alginate, propylene glycol alginate, propylene glycol ester alginate, ammonium alginate, Is used more preferably.
As described above, since the nanofiber layer of the present invention forms an acid-base complex, the polysaccharide polymer having a cationic functional group together with the anionic functional group-containing polysaccharide polymer is used, and the cationic functional group Is preferably a chitosan or a derivative thereof. The chitosan is obtained by deacetylating an acetamide group (-NHCOCH 3 ) of N-acetylglucosamine which constitutes a repeating unit of chitin contained in the skeleton of crustaceans such as crabs and shrimp, to produce an amino group (-NH 2 ) It is known that the amino group (-NH 2 ) present in the chitosan or its derivative is present in the polysaccharide polymer having the anionic functional group because it is a cationic natural polymer converted and has no toxicity to the living body and excellent skin moisturizing and antibacterial activity Is bonded with a carboxyl group (-COOH) to form an acid-base complex.
At this time, the degree of deacetylation of the acetamide group (-NHCOCH 3 ) of the chitosan or its derivative is preferably 75 to 100%. When the degree of deacetylation is less than 75%, the solubility of the chitosan or its derivative is lowered In addition, since the reaction site for forming a complex with a polysaccharide polymer having an anionic functional group is reduced and it may be difficult to form a stable acid-base complex, a degree of deacetylation of 75% or more is used.
Further, the water-soluble polymer is essentially contained in the nanofiber layer of the present invention. By including the water-soluble polymer in the nanofiber layer, the nanofiber sheet including the nanofiber layer is positively adhered to the skin of the nanofiber sheet, Thereby contributing to improving adhesion. That is, when the nanofiber sheet is applied to the skin together with the water-containing liquid, the water-soluble polymer of the nanofiber layer dissolves by the contact between the nanofiber sheet and the water to act as a binder, and the contact between the nanofiber sheet and the skin is maintained . In addition, since the nanofiber layer has a cross-linked structure in the form of an acid-base complex from a polysaccharide polymer having an anionic functional group and a polysaccharide polymer having a cationic functional group, the nanofiber retains its fiber form even after the water soluble polymer is dissolved.
As the water-soluble polymer, any one selected from the group consisting of polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, and mixtures thereof, which is excellent in biocompatibility and widely employed in biomedical engineering, is preferably used. The invention improves the skin adhesion of the nanofiber sheet by imparting tackiness to the nanofiber sheet containing the water-soluble polymer without using a tackifier component harmful to the human body in the past.
On the other hand, the nanofiber layer preferably comprises (a) 20 to 99% by weight of a complex of a polysaccharide polymer having an anionic functional group and a polysaccharide polymer having a cationic functional group and 1 to 80% by weight of a water soluble polymer If the content of the complex forming the nanofiber layer is less than 20 wt% (the content of the water-soluble polymer is more than 80 wt%), a stable acid-base complex is not formed and the nanofiber is dissolved in the water- If the content of the water-soluble polymer constituting the nanofiber layer is less than 1% by weight (the content of the complex is more than 99% by weight), the adhesion may deteriorate and the skin adhesion of the nanofiber sheet may deteriorate.
In addition, the nanofiber sheet according to the present invention may further comprise a functional cosmetic ingredient commonly used for skin cosmetics. The functional cosmetic ingredient is harmless to the human body and contained in the nanofiber sheet, Whichever is suitable for use as long as it can exert its inherent functions, can be suitably used. However, any one selected from the group consisting of a moisturizer, a whitening agent, a wrinkle-reducing agent, an antioxidant, and a mixture thereof is preferably used.
The nanofiber according to the present invention preferably has an average diameter of 10 to 1,000 nm. As shown in FIG. 1, the nanofiber having an average diameter within the above range has a surface area larger than that of microfibers, It is possible to effectively utilize functional cosmetic ingredients because of its large area, and to improve skin adhesion. The thickness of the nanofiber sheet of the present invention is preferably 0.05 to 1,000 μm. If the thickness of the nanofiber sheet is less than 0.05 μm, it is not easy to maintain mechanical strength when a separate support is not used. If the thickness exceeds 1,000 占 퐉, adhesion with the skin may deteriorate and functional cosmetic ingredients contained in the nanofiber sheet may not be efficiently released.
In addition, in the present invention, a mask pack having a desired shape including the above-described nanofiber sheet can be easily manufactured.
The present invention also provides a method for preparing a spinning solution 1, comprising: I) obtaining a spinning solution 1 in which a polysaccharide polymer having an anionic functional group and a water-soluble polymer are mixed; II) obtaining a spinning solution 2 in which a polysaccharide polymer having a cationic functional group and a water-soluble polymer are mixed; And III) supplying and discharging the spinning solutions 1 and 2 to respective spinning nozzles and electrospinning the spinning solution onto one collector plate to form a nanofiber layer.
The polysaccharide polymer having an anionic functional group, the polysaccharide polymer having a cationic functional group and the water-soluble polymer used for obtaining the spinning solutions 1 and 2 may be as described above.
As shown in FIG. 2, in step III), spinning solutions 1 and 2 are supplied to and discharged from spinning nozzles and electrospun to one collector plate to form a nanofiber layer having a crosslinked structure in the form of an acid- And the water-soluble polymer exhibiting tackiness is entangled in the nanofiber layer. Due to these technical features, it is possible to form a single nanofiber layer without a separate support, the peeling phenomenon of the nanofiber layer does not easily occur, and a functional cosmetic ingredient can be carried at a high concentration, .
In addition, in order to obtain a uniform fiber phase as in an ordinary electrospinning process, the formation of the jet must be continuously and stably performed in the electrospinning process. In the present invention, the composition of the spinning solutions 1 and 2, the relative humidity, the spinning temperature, The conditions such as the applied voltage, the spinning liquid discharge speed, and the radiating distance (distance from the end of the spinning nozzle to the current collecting plate) are appropriately adjusted.
That is, the electrospinning may be performed at a relative humidity of 20 to 40%, a spinning temperature of 25 to 70 占 폚, a spinning time of 15 to 40 hours, an applied voltage of 10 to 30 kv, a spinning solution of 1 to 2 And a radiation distance of 10 to 20 cm. Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings.
[Example] Production of nanofiber sheet of an acid-base complex structure
500 g of deionized water was added to a 1 L three-necked flask equipped with a stirrer, and 5 g of sodium alginate and 5 g of polyethylene oxide were added and gradually dissolved at 60 ° C to obtain a spinning solution 1. On the other hand, 5 g of chitosan and 5 g of polyethylene oxide were dissolved in 500 g of a 3% by weight acetic acid aqueous solution at 25 占 폚 to obtain a spinning solution 2. A nanofiber sheet of an acid-base complex structure was prepared by electrospinning the spinning solutions 1 and 2, respectively, on one collector plate under the following conditions.
(Relative humidity: 30%, spinning time: 32 hours, applied voltage: 18 kV, discharge rate of spinning solution 1 and 2: 0.5 ml / hr, scattering distance: 15 cm)
[Comparative Example 1] Production of nanofiber sheet having no acid-base complex structure
A nanofiber sheet was prepared in the same manner as in Example except that only the spinning solution 1 of the above example was used.
[Comparative Example 2] Production of nanofiber sheet having no acid-base complex structure
A nanofiber sheet was prepared in the same manner as in Example except that only the spinning liquid 2 of the above-mentioned example was used.
FIG. 3 is a photograph of a nanofiber formed by electrospinning according to the above embodiment, and FIG. 4 is a scanning electron microscope photographing the surface of the nanofiber formed by electrospinning according to the embodiment SEM). As a result, a nanofiber sheet having an entangled water-soluble polymer tacky on a nanofiber layer having a cross-linked structure of a defect-free acid-base complex type was produced by forming a jet stably in the electrospinning process .
In addition, the nanofiber sheet of the acid-base complex structure and the nanofiber sheet having no acid-base complex structure prepared in Examples of the present invention and Comparative Examples 1 and 2 were produced in the form of a normal mask pack, The skin adhesion force and water retention time of the cellulose nonwoven sheet type mask pack of the present invention were tested. As a result, the water-soluble polymer exhibiting tackiness was entangled in the nanofiber layer having the crosslinked structure of the acid- it was confirmed that the mask pack made from the nanofiber sheet of the entangled configuration had the best skin adhesion and water retention time and the results are shown in Table 1 below.
1) A mask pack sample was attached to the face for one hour for five subjects, and the degree of skin adhesion was evaluated as follows: ⊚ (very good), ◯ (good), × (poor)
2) Time required for 80% water evaporation
Therefore, the nanofiber sheet produced according to the present invention has excellent biocompatibility and improved skin adhesion, and since the nanofiber layer has a crosslinked structure in the form of an acid-base complex, the nanofiber layer can not be peeled off even after the nanofiber sheet is formed, Can be maintained for a long time.
Claims (16)
(b) a nanofiber layer made of a water-soluble polymer.
II) obtaining a spinning solution 2 in which a polysaccharide polymer having a cationic functional group and a water-soluble polymer are mixed; And
III) forming a nanofiber layer by supplying and discharging the spinning solutions 1 and 2 to respective spinning nozzles and electrospunning the spinning solutions 1 and 2 on a single current collector plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150023814A KR20160101374A (en) | 2015-02-17 | 2015-02-17 | Nanofiber sheet and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150023814A KR20160101374A (en) | 2015-02-17 | 2015-02-17 | Nanofiber sheet and manufacturing method thereof |
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| KR20160101374A true KR20160101374A (en) | 2016-08-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021137246A1 (en) * | 2019-12-31 | 2021-07-08 | Chairperson, Ipr Cell (Prof. Abanti Sahoo) | Nano fibrous polyelectrolyte complex for rapid control of haemorrhage |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100128142A (en) | 2009-05-27 | 2010-12-07 | 주식회사 지니메디 | Mask pack set using electric repulsive force |
| KR20110080066A (en) | 2010-01-04 | 2011-07-12 | 부산대학교 산학협력단 | Skin beautifying sheet and method for preparation thereof |
-
2015
- 2015-02-17 KR KR1020150023814A patent/KR20160101374A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100128142A (en) | 2009-05-27 | 2010-12-07 | 주식회사 지니메디 | Mask pack set using electric repulsive force |
| KR20110080066A (en) | 2010-01-04 | 2011-07-12 | 부산대학교 산학협력단 | Skin beautifying sheet and method for preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 특허문헌 3 미국특허공보 제4,582,865호 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021137246A1 (en) * | 2019-12-31 | 2021-07-08 | Chairperson, Ipr Cell (Prof. Abanti Sahoo) | Nano fibrous polyelectrolyte complex for rapid control of haemorrhage |
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