WO2016137293A1 - Method for manufacturing functional extract-containing polyvinylalcohol nanofibrous non-woven fabric by heterogeneous saponification of polyvinylacetate nanofibrous non-woven fabric - Google Patents

Abstract

The present invention relates to a method for manufacturing a functional extract-containing polyvinylalcohol nanofibrous non-woven fabric, which has an improved specific surface area by creases and nanopores formed in a surface thereof and, specifically, to a method for manufacturing a functional extract-containing polyvinylalcohol nanofibrous non-woven fabric having creases and nanopores formed in a surface thereof, the method comprising a step of, while immersing a functional extract-containing polyvinylacetate nanofibrous non-woven fabric in a first solvent capable of maintaining the non-woven fabric form of the functional extract-containing polyvinylacetate nanofibrous non-woven fabric, saponifying the functional extract-containing polyvinylacetate nanofibrous non-woven fabric to convert the functional extract-containing polyvinylacetate nanofibrous non-woven fabric into a functional extract-containing polyvinylalcohol nanofibrous non-woven fabric having creases and nanopores formed in a surface thereof.

Description

Method for producing polyvinyl alcohol nanofiber nonwoven fabric containing functional extract by heterogeneous saponification of polyvinyl acetate nanofiber nonwoven fabric

The present invention relates to a method for producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric having wrinkles and nanopores formed on the surface thereof to improve a specific surface area, wherein the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric can maintain a nonwoven form. Saponifying the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric in a state impregnated with the first solvent to convert the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric to a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric; It relates to a method for producing a vinyl alcohol nanofiber nonwoven fabric.

In the high-tech industry to lead the 21st century, new concept materials that combine multi-functions such as environmental friendliness, ultra-light weight, extreme functionality, and complex functionality are required. Much attention is paid to the manufacturing technology of nanofibers having diameters of several to several hundred nanometers (nm).

To date, nanofibers are oriented simultaneously with polymerization of polymers in nanofibers, nanosized diameter nanoreactors formed by electrospinning of nanofibers, polymer solutions or melts formed using phase separation of each component of the block copolymer. Nanofibers, which are obtained, and carbon nanofibers obtained by carbonizing composite fibers of two polymers which are incompatible with each other and have a large degree of carbonization and are carbonized are being studied.

Considering the economic feasibility and simplicity of the manufacturing process, and the application of various product technologies, the production of nanofibers by electrospinning is considered as the most powerful technology.

Electrospinning is a method of manufacturing a non-woven fabric by a method in which a polymer solution is placed in a syringe with a capillary tip to apply positive (+) charges or negative (-) charges, and to apply an opposite charge to a collector. It can be said to be the most useful way to prepare. When an electric field of more than the same intensity as the surface tension is applied to the polymer solution formed in the hemispherical shape at the capillary tip by the surface tension, the hemispherical polymer solution gradually forms a conical Taylor cone in the direction of the integrated plate. jet in the form of a jet). The single jet injected causes scattering, which is divided into many filaments due to charge repulsion, and thus forms a porous nonwoven nanofiber in the form of a nonwoven fabric having a nano diameter.

First manufactured by German Hermann in 1931 (German Patent No. 685,048 (1931)), polyvinyl alcohol (PVA) fiber has been in the limelight as clothing and industrial fiber for more than 70 years. have. In particular, recently, it has been used as a high functional material such as a polarizing film, a medical polymer and a contact lens.

According to U.S. Patent No. 4,963,138, ultra high molecular weight polyvinyl acetate (PVA) having an intrinsic viscosity of more than 5 (dl / g) was synthesized by completely saponifying ultra high molecular weight polyvinyl acetate obtained by initiating vinyl acetate with ultraviolet rays and bulk polymerization at various low temperatures. , Imai, et al. [K. Imai, T. Shiomi, N. Oda, and H. Otsuka, J. Polym. Sci .: Polym. Chem. Ed., 24, 3225 (1986)] prepared a high molecular weight PVA from polyvinyl acetate obtained by bulk polymerization of vinyl acetate at 60 ° C. with a small amount of azobisisobutyronitrile.

In addition, Nakamae et al. [K. Nakamae et al., Polymer, 33, 2581 (1992), described the high shift of 63% of the alternating diad group by saponifying a precursor obtained by polymerizing ADMVN with an ultraviolet irradiation solution of vinyl trifluoride acetate at -78 ° C. An array PVA was prepared, and in Korean Patent No. 10-1024173, poly (vinyl pivalate) prepared by any one polymerization method selected from the group consisting of bulk copolymerization, solution copolymerization, emulsion copolymerization and suspension copolymerization of vinyl pivalate and vinyl acetate A high strength microfibrillated PVA short fiber was prepared by adding a specific alkali saponifier to a copolymer and simultaneously performing mechanical shearing with various kinds of stirrers and stirring speeds.

Further, according to Japanese Patent Application Laid-Open No. 4-108109, saponification of a mother polymer prepared by polymerizing a monomer having a side chain group causing steric hindrance to prepare a high molecular weight PVA rich in alternating array groups, and then separating, washing and After drying, the resultant was dissolved in a solvent to spin the solution, which was then stretched and dried to obtain PVA fibers.

However, the polyvinyl alcohol fiber production methods reported by the saponification process so far have been directed to the production of a fiber form having a micro-thickness, and were not manufactured in the form of nanofiber nonwoven fabrics. In addition, the manufacturing methods of the polyvinyl alcohol nano nonwoven fabrics reported so far have not been associated with changing the surface of the polyvinyl alcohol nano fiber nonwoven fabrics, and in particular, the method of controlling the roughness of the surface of the polyvinyl alcohol nano fiber nonwoven fabrics. Nothing was reported. Furthermore, there has been no report on how to control the roughness of the surface of the polyvinyl alcohol nanofiber nonwoven fabric with the properties of the natural extract.

Accordingly, the present inventors approached in various ways to maximize the specific surface area of the nanofiber nonwoven fabric and to provide functionality such as antioxidant and contact dermatitis inhibitory effect of the functional extract, polyvinyl acetate spinning solution containing a functional extract After the production of nanofiber non-woven fabric by using the as a starting material and electrospinning, and then converted to a polyvinyl alcohol containing functional natural extract through a non-uniform saponification process, wrinkles and nano pores are formed on the surface, the specific surface area is improved At the same time confirmed that it can give the characteristics of the functional extract to complete the present invention.

It is an object of the present invention to provide a polyvinyl alcohol nanofiber nonwoven fabric having a wrinkle and nanopores formed on a surface thereof, to which a specific surface area is improved, and at the same time, to which functionality of a functional natural extract is provided.

In order to achieve the above object, the present invention contains a functional extract-containing polyvinyl acetate nanofiber nonwoven fabric by saponifying the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric in the state impregnated in the first solvent capable of maintaining the nonwoven form Provided is a method for producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric having wrinkles and nano pores formed on its surface, including converting the polyvinyl alcohol nanofiber nonwoven fabric.

Polyvinyl alcohol (PVA) is a semicrystalline synthetic polymer having a hydroxyl group capable of forming a hydrogen bond, and cannot be synthesized by direct polymerization of a vinyl alcohol monomer. ) Are synthesized and hydrolyzed with alkalis or acids. Polyvinyl acetate and polyvinyl alcohol have different kinds of solvents that can be dissolved. Specifically, polyvinyl acetate is dissolved in methanol, ethanol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, ethyl acetate, methylene chloride, methyl ethyl ketone, toluene, ethylene glycol diacetate, and the like. Can be difficult to dissolve in water. In addition, polyvinyl alcohol is soluble in water but difficult to dissolve in an organic solvent. The functional extract may be obtained from various extraction solvents, and the extraction solvent may vary depending on the type of the functional ingredient. Accordingly, in preparing nanofiber nonwoven fabric by electrospinning polyvinyl alcohol, a functional extract using an organic solvent as an extraction solvent may be difficult to prepare as a uniform spinning solution together with polyvinyl alcohol.

In the present invention, as shown in Figure 1 by dissolving a functional natural extract with polyvinyl acetate to prepare a spinning solution, by producing a polyvinyl alcohol nanofiber non-woven fabric by electrospinning and heterogeneous saponification, organic solvent is extracted solvent There is an advantage to produce a polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract to. In addition, even in the case of a functional extract using water as an extraction solvent, it can be produced as a spinning solution together with polyvinyl acetate soluble in alcohol such as methanol and ethanol. Accordingly, the present invention can produce a polyvinyl alcohol nanofiber nonwoven fabric uniformly containing functional extracts obtained from various extraction solvents.

Furthermore, the method for producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric according to the present invention has a wrinkled form and nano pores on the surface thereof, thereby improving the specific surface area compared to the polyvinyl alcohol nanofiber nonwoven fabric having a smooth surface. A polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract of a structure can be prepared, and the nanofiber nonwoven fabric can be applied to implants, synthetic fibers, packaging materials, coating agents, adhesives, polarizing films, and the like to achieve an improved effect.

In the present invention, the functional natural extract-containing polyvinyl acetate nanofiber nonwoven fabric may be prepared by electrospinning a spinning solution in which the functional natural extract and polyvinyl acetate are dissolved in a second solvent. Specifically, the high-viscosity spinning solution obtained by dissolving the functional extract and polyvinyl acetate in the second solvent is spun by using an electrospinning method, followed by an electrospinning method to volatilize the second solvent to produce a nanofiber nonwoven fabric. Can be prepared.

As used herein, the term "functional natural extract (or functional extract)" means a functional substance obtained by extraction treatment of a natural product or a synthetic compound of natural products. The functional natural extract may be prepared by using the extract itself and the extract, such as an extract obtained by an extraction treatment, a diluent or concentrate of the extract, a dried product obtained by drying the extract, a crude or purified product of the extract, or a mixture thereof. Extracts of all possible formulations.

In the present invention, as an extract raw material of the functional extract may be used for bokyeong, sorghum and the like. In one embodiment of the present invention was used a mixture (1: 1, w / w) of the Fukryeong methanol extract and sorghum methanol extract, limited to the preparation examples, examples and experimental examples of The mixture is referred to as a functional natural extract.

The scientific name of Poria cocos (茯) is included Ria Caucus (Poria cocos) Taxonomic truly basidiomycete steel, copper basidiomycete subclass (Subclass mogyun), the Democratic name Mushrooms neck hole sheets and mushroom belongs to a. It is a fungus that grows mainly from the roots of pine trees. It is called Baekbok-ryeong if it is white, and red peak if it is pink. Since ancient times, it has been said that it is good for health and stabilization, and not only has the effect of stabilizing heat, but also warms the body. It is effective for peptic ulcer, muscle spasms, thirst, vertigo, mental anxiety and insomnia. It is effective in tonic, diuresis and sedation as a herbal medicine, and has been used for kidney disease, cystitis and urethritis. In addition, contact dermatitis inhibitory effect has been found.

Fukryeong extract has a tonic effect as well as alleviating gastric dysfunction. In oriental medicine, Fukryeong extract is classified as a sedative and diuretic. In addition, Fukryeong extract is used as one of the important components of herbal preparations for energy recovery. Studies and experiments related to the pharmaceutical efficacy of Bok-Ryong extract in recent years have shown that Bok-Ryong extract has excellent efficacy in suppressing tumors and improves immunity and protects the stomach and intestines of people suffering from chronic diseases. Turned out.

Sorghum (sorghum, Sorghum bicolor L. Moench) is a perennial herb that is an annual crop of flowering plants and is mainly consumed for food in Korea. Sorghum contains a large amount of functional ingredients such as dietary fiber and phenolic compounds, and phenolic compounds are composed of flavonoids, tannins, and phenolic acids, most of which are known as flavonoids, and many studies on physiological functions of sorghum have been reported recently. Sorghum extracts are known to exhibit potent antioxidant activity.Study on the functionalities of sorghum extracts of 25 kinds of sorghum extracted with methanol and sequentially solvent fractionation, assayed for antioxidant and antimicrobial activity, and measured the antioxidant activity of sorghum anthocyanin. There are reports of phenolic components such as phenolic acid, flavonoids and tannins contained in research and sorghum.

The functional natural extract of the present invention can be extracted from natural, hybrid or variety plants of the respective plants of interest, and can be extracted from plant tissue cultures and their compounds.

In the extraction of the functional extract of the present invention, the extraction method is not particularly limited and may be extracted according to a method commonly used in the art. Non-limiting examples of the extraction method, hot water extraction method, ultrasonic extraction method, filtration method, reflux extraction method and the like, these may be carried out alone or in combination of two or more methods.

In the present invention, the type of the extraction solvent used for the extraction of the functional extract may be variously selected as described above including water and an organic solvent, and preferably, a solvent capable of dissolving polyvinyl acetate, ie, a second solvent. It may be the same as the solvent, or soluble and / or miscible thereto. Non-limiting examples of such extraction solvents include water; C ₁ to C ₄ lower alcohols such as methanol, ethanol, propyl alcohol and butyl alcohol; Polyhydric alcohols such as glycerin, butylene glycol, and propylene glycol; Hydrocarbon solvents such as methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether and dichloromethane; Or a mixture thereof can be used, Preferably, water, a lower alcohol, a polyhydric alcohol, a hydrocarbon solvent can be used individually or in mixture of 2 or more types. More preferably, the extraction solvent may be the same as the second solvent. When the extraction solvent and the second solvent are the same, the extraction solvent contained in the functional extract can be used as it is, without further treatment, and the polyvinyl acetate can be dissolved using the solvent used as the extraction solvent. Since the second solvent can be reduced, and unnecessary interaction between the extraction solvent and the second solvent does not occur, the reaction efficiency can be improved.

The extract extracted by heat or cold extraction in the present invention is filtered to remove the suspended solid particles, for example, by filtering the particles using a nylon or the like, or filtered using a freeze filtration method, or use them as it is or lyophilization, hot air drying, It can be dried by spray drying or the like.

In the present invention, the concentration of the functional extract in the polymer solution may be 0.05 wt.% To 10 wt.%. When the concentration is less than 0.05 wt.%, It may be difficult to exhibit the functionality of the functional extract, and when it exceeds 10 wt.%, The amount of the functional extract may be too large to control the viscosity of the polymer solution and the dispersion of the functional extract, making it difficult to form a film. It is difficult, and there is a problem that the functional extract is unevenly distributed in the produced film.

In the present invention, polyvinyl acetate can be prepared and used by the method of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization. Particularly, bulk polymerization has a merit that relatively high molecular weight polyvinyl acetate can be obtained because the probability of chain transfer is low since only monomer is present in the polymerization system.

In the present invention, the second solvent is not limited as long as it is a solvent capable of dissolving polyvinyl acetate, but preferably methanol, ethanol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, ethyl acetate, and methylene. Chloride, methyl ethyl ketone, toluene, ethylene glycol diacetate or a mixed solvent thereof.

The concentration of polyvinyl acetate in the spinning solution may be 1 wt.% To 30 wt.% As a factor related to the viscosity of the spinning solution. At a concentration of less than 1 wt.% Of the polyvinyl acetate, the solution is too thin so that the solution is difficult to spray, and even when sprayed, it is not easy to form the nanofiber nonwoven fabric. If it is more than 30 wt.%, It is difficult to form a nanofiber nonwoven fabric due to its high viscosity.

The functional extract and polyvinyl acetate can be dissolved with stirring in a bath for 0.1 hours to 5 hours at a temperature of 30 ℃ to 50 ℃. Preferably it may be stirred for 30 minutes at a temperature of 40 ℃. When used out of the above range, the functional extract and / or polyvinyl acetate may not be completely dissolved, resulting in a problem that uniform spinning may not be achieved.

In addition, the production method according to the present invention can be stabilized by leaving the solution for 0.5 hours to 5 hours at room temperature of 20 ℃ to 35 ℃ to stabilize the spinning solution. Preferably it can be stabilized for 1 hour at a temperature of 20 ℃.

Then, by electrospinning, the polymer spinning solution containing the functional extract and polyvinyl acetate is released from the capillary, while the solvent is volatilized and the fiber having a diameter of several tens to thousands of nanometers while the released polymer spinning solution flies in the air. May be stacked in a three-dimensional network structure to form nanofibers in the form of a nonwoven fabric.

The electrospinning may be performed at a distance of 1 cm to 30 cm between a capillary tube and a collector and at an applied voltage of 5 kV to 40 kV. More preferably, the distance between the capillary (Tip) and the collector (Collector) is 10 cm, it can be carried out under the conditions of an applied voltage of 15 kV to 17.5 kV.

When the applied voltage of the electrospinning apparatus is less than 5 kV, there is a problem that a bead phase and a fiber phase are mixed and the fiber diameter is not uniform. When the voltage exceeds 40 kV, the diameter of the fiber is Although reduced, there is a problem that the intermittently formed nanofibers can be broken form.

If the distance between the capillary tube and the collector is less than 1 cm, the distance is so close that the spinning solution may not be able to stretch out, resulting in a large fiber diameter. There is a problem that can represent the form. If the distance between the capillary (Tip) and the collector (Collector) is more than 30cm, there is a problem that may not be radiated into the collector due to the viscosity of the polyvinyl acetate.

The concentration of the spinning solution, the applied voltage, and the distance between the capillary and the integrated plate should be determined in consideration of the type of electrospinning apparatus, the required properties and the functional improvement. If used out of the above range may cause a problem that is difficult to manufacture a non-woven fabric having a nano diameter.

In the present invention, by electrospinning with a conventional electrospinning apparatus, it is spun and stacked on a collector and collected in the form of a nonwoven fabric having a three-dimensional network structure.

Specifically, a conventional electrospinning device generates a syringe for injecting a spinning solution (polymer solution), a tip for discharging a spinning solution, a collector for collecting fibers to be disposed at the bottom of the tip, and a high voltage as shown in FIG. 2. It consists of a voltage generator for supplying the supply and the device for delivering the generated voltage to the spinning solution.

A continuous voltage is supplied to the polymer solution contained in the syringe so that the spinning solution is spun and stacked onto the collector under high voltage through the tip at the tip of the syringe to form a nonwoven fabric.

In the embodiment of the present invention, the polyvinyl acetate solution containing the functional extract dissolved in methanol, as shown in Table 1, by adjusting the concentration of the polyvinyl acetate and functional extract and by adjusting the voltage during electrospinning to find the optimum conditions A polyvinyl acetate nanononwoven fabric containing the functional extract was prepared.

The functional extract-containing polyvinyl acetate nanofiber nonwoven fabric is a solvent capable of maintaining the nonwoven fabric form, that is, the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric is impregnated in a state in which the first solvent is impregnated with the functional extract-containing polyvinyl alcohol nano. By converting to a fiber nonwoven fabric, a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric having wrinkles and nanopores formed on its surface can be produced.

The manufacturing method of the present invention is not saponification in the state of dissolving the functional extract and polyvinyl acetate in the second solvent, but instead saponifying the polyvinyl acetate nanofiber nonwoven fabric containing the functional extract and maintaining the nonwoven form. A functional natural extract-containing polyalcohol vinyl nanofiber nonwoven fabric having wrinkles and nano pores formed on the surface of the fibrous nonwoven fabric is formed. Therefore, it is important to use a solvent, that is, a first solvent, to maintain the functional extract-containing polyvinyl acetate nanofiber nonwoven form during saponification.

Specifically, the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric is impregnated with a first solvent to convert -OCOCH ₃ group of the polyvinyl acetate nanofiber nonwoven fabric into -OH group by heterogeneous saponification, and thus the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric Can be prepared.

In the present invention, the first solvent may be an acid solution or an alkaline solution, including a dispersant and a swelling agent. The dispersing agent and the swelling agent serve as a catalyst so that the non-uniform surface saponification can occur by saponifying only the surface of the polyvinyl acetate nanofiber nonwoven fabric containing the functional natural extract while maintaining the nonwoven form.

The acid in the acid solution for saponification may be hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof, and the alkali in the alkaline solution for saponification may be sodium chloride, sodium hydroxide, potassium hydroxide, sodium bromide, sodium iodide or mixtures thereof. This is not restrictive.

The dispersant may be sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate or mixtures thereof.

In addition, the swelling agent may be methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone or a mixture thereof. Preferably, methanol can be used that is easy to acquire, inexpensive, has a low boiling point, and is easy to handle.

The acid solution may be hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof; Any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, or mixtures thereof; And water, preferably distilled water may be mixed and dissolved, but is not limited thereto.

More preferably, the acid solution is 1 g to 30 g of hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof based on 1 g of the functional natural extract-containing polyvinyl acetate nanofiber nonwoven fabric; 1 g to 30 g of any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; 1 g to 30 g of any swelling agent selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone, or mixtures thereof; And 10 ml to 500 ml of water may be mixed and dissolved.

The alkaline solution may be sodium chloride, sodium hydroxide, potassium hydroxide, sodium bromide, sodium iodide or mixtures thereof; Any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, or mixtures thereof; And water, preferably distilled water may be mixed and dissolved, but is not limited thereto.

More preferably, the alkaline solution comprises 1 g to 30 g of sodium chloride, sodium hydroxide, potassium hydroxide, sodium bromide, sodium iodide or a mixture thereof based on 1 g of the polyvinyl acetate nanofiber nonwoven fabric containing the functional extract; 1 g to 30 g of any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; 1 g to 30 g of any swelling agent selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), benzene, acetone, or mixtures thereof; And 10 ml to 500 ml of water may be mixed and dissolved.

More specifically, the alkaline solution is sodium chloride; Sodium sulfate; Methanol; And water, preferably distilled water may be mixed and dissolved, but is not limited thereto.

When the acid or base type and content of the acid solution or the alkali solution is not satisfied, it may not be easy to form wrinkles on the surface of the nanofiber nonwoven fabric as the -OCOCH ₃ group is converted to the -OH group.

The degree of saponification of the present invention is preferably 60% to 99.9%. Here, the "saponification degree" shows the ratio of the unit actually saponified to a vinyl alcohol unit among the units obtained by converting into a vinyl alcohol unit by saponification, and can be measured by the method of JIS base. Specifically, it can be expressed as the ratio of the number of moles of the compound converted to -OH group to the number of moles of the compound having a total -OCOCH ₃ group.

In the present invention, saponification of the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric may be performed at a temperature of 5 ° C. to 80 ° C. for 1 hour to 6 hours. Preferably it can be saponified for 1 to 6 hours at a temperature of 30 to 40 ℃, most preferably saponified for 3 hours at a temperature of 40 ℃.

The saponification step is performed at a temperature range of 5 ° C. to 80 ° C. to maximize the activation of methanol, for example, as a swelling agent that serves as a catalyst. The boiling point of methanol is about 64.7 ° C. At higher temperatures, methanol evaporates. If the temperature of the saponification step is less than 5 ℃ degree of saponification is about 50%, the degree of saponification may be 99.9% at 50 ℃. In the present invention, a polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract having a saponification degree of 99.9% is formed even if the temperature is raised to 80 ° C. unless the boiling point of the swelling agent is exceeded.

In addition, the saponification in the saponification step for 1 to 6 hours is to prepare a polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract having a saponification degree of 60% to 99.9%. As the time for introducing the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric into the first solvent becomes longer, the ratio of -OCOCH ₃ group to -OH group may be increased. If the saponification time is less than 1 hour, the degree of saponification is about 30%, and the saponification reaction time is insufficient to achieve a saponification degree of 60% to 99.9%. In addition, when the saponification reaction is carried out for 6 hours or more, a polyvinyl alcohol nanofiber nonwoven fabric containing a saponification degree of 99.9% can be prepared, so that the saponification time also contains a 99.9% saponification degree of functional extract. Polyvinyl alcohol nano fiber nonwovens can be prepared. However, it is not economical to carry out the reaction for more than 6 hours.

As another aspect, the present invention provides a polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract having wrinkles formed on the surface of the nonwoven fabric and having nanopores having a porosity of 50% to 95%.

The depth of the wrinkles of the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric may be formed of 10 nm to 10 ㎛. The depth of the wrinkles of the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric may be formed from 10 nm to 10 ㎛. When the depth of wrinkles of the polyvinyl alcohol fiber nonwoven fabric is less than 10 nm, the effect of increasing the specific surface area of the polyvinyl alcohol nanofiber nonwoven fabric due to the wrinkles formed on the surface is insignificant, and the wrinkles of the polyvinyl alcohol nanofiber nonwoven fabric When the depth of more than 10 ㎛ has a disadvantage that the wrinkles of the polyvinyl alcohol nanofiber nonwoven fabric is too large to form a fiber, even if the fiber is formed, the physical properties are lowered.

Wrinkles are formed on the surface of the nonwoven fabric of the present invention, and the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric having nanopores having a porosity of 50% to 95% can be prepared by the manufacturing method according to the present invention. . Compared to the conventional polyvinyl alcohol nanofiber nonwoven fabric having a smooth surface, in the case of the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric produced through the heterogeneous saponification reaction according to the present invention, the uneven wrinkles on the nonwoven surface have a directionality. It is not visible but has many folded shapes to maximize the specific surface area of the nonwoven fabric. Therefore, the functional extract content may be increased in the polyvinyl alcohol nanofiber nonwoven fabric, and the functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric may increase the contact area with a material in contact with the nanofiber nonwoven fabric. Interactions such as contact strength and mass transfer can also have beneficial effects.

As described above, the polyvinyl alcohol nanofiber nonwoven fabric containing a functional extract of a novel form having wrinkles formed on the nonwoven fabric and having nanopores having a porosity of 50% to 95% has an improved specific surface area such as filter material, reinforcing fiber, It can be used in a variety of fields, such as carriers, implants, synthetic fibers, packaging materials for culturing biological tissues can be expected to better properties.

In addition, the prepared functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric may be given the functionality of natural extracts such as antioxidant, contact dermatitis inhibitory effect.

In particular, the polyvinyl alcohol nanofiber nonwoven fabric of the conventional polyvinyl alcohol nanofibrous nonwoven fabric of the functional extract prepared by the non-uniform saponification reaction in the present invention compared to the cylindrical shape of each of the fibrous crushed or crumpled The uneven wrinkles are not directional but have many folded shapes, maximizing the specific surface area of the nanofiber nonwoven fabric.

According to the production method of the present invention, wrinkles are formed on the surface of the polyvinyl alcohol nanofiber nonwoven fabric, so that the specific surface area is improved and at the same time, a new polyvinyl alcohol nanofiber nonwoven fabric provided with the functionality of the functional extract can be produced.

Figure 1 shows a schematic diagram of the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric of the present invention after the saponification step is made of a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric.

Figure 2 shows a schematic diagram of the electrospinning apparatus of the present invention.

3 is a scanning electron micrograph of a non-uniform saponified polyvinyl alcohol nanofiber nonwoven fabric prepared according to an alkali solution amount. The temperature is the same at 40 ° C saponification time 3 hours.

(a) NaOH (5 g), Na ₂ SO ₄ (5 g), MeOH (5 g)

(b) NaOH (10 g), Na ₂ SO ₄ (10 g), MeOH (10 g)

Figure 4 is a scanning electron micrograph of the non-uniform saponified polyvinyl alcohol nanofiber nonwoven fabric prepared according to the saponification time. Alkaline solution required for saponification is the same with NaOH (10 g), Na ₂ SO ₄ (10 g), MeOH (10 g), temperature 40 ℃.

(a) 1 hour saponification time

(b) saponification time 6 hours

5 is a view showing the results of the patch test to evaluate the skin safety by applying the prepared functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric to the skin.

6 is a table showing the criteria for the determination of the International Contact Dermatitis Study Group.

7 is a scanning electron micrograph of the prepared non-uniform saponified polyvinyl alcohol nanofiber nonwoven fabric.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples. Among the compounds used below, starting materials and reaction reagents were used as reagents of Aldrich. All solvents were pure and used without drying or purification.

In Preparation Examples 1 to 14, an experiment for preparing a polyvinyl acetate nanofiber nonwoven fabric containing a functional extract was performed. The polyvinyl acetate spinning solution containing the functional extract dissolved in methanol was prepared by adjusting process variables to prepare the polyvinyl acetate nanofiber nonwoven fabric containing the functional extract under optimum conditions. At this time, as a functional extract, a mixture (1: 1, w / w) of the Boeryeong methanol extract and the sorghum methanol extract was used, and it is referred to as a functional natural extract only in preparation examples, examples and experimental examples.

Preparation Example 1 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

3 wt.% Polyvinyl acetate was added to a 99% purity methanol solvent (38.315 ml), stirred at 40 ° C. for 30 minutes, and then stabilized for 1 hour. 1 wt.% Functional natural extract was added to the solution and 30 minutes at 40 ° C. After stirring for a while, the prepared polyvinyl acetate spinning solution containing the functional natural extract was dried at room temperature for about an hour, and then the nanofiber nonwoven fabric after electrospinning by controlling the voltage (17.5 kV) and the distance (10 cm) between the tip and the collector. Was prepared.

Preparation Example 2 Preparation of Polyvinyl Acetate Nanofiber Nonwoven Fabric Containing Functional Natural Extract

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 4 wt.%.

Preparation Example 3 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 5 wt.%.

Preparation Example 4 Preparation of Polyvinyl Acetate Nanofiber Nonwoven Fabric Containing Functional Natural Extract

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 6 wt.%.

Preparation Example 5 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 7 wt.%.

Preparation Example 6 Preparation of Polyvinyl Acetate Nanofiber Nonwoven Fabric Containing Functional Natural Extract

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 8 wt.%.

Preparation Example 7 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1 except that the concentration of polyvinyl acetate was adjusted to 9 wt.%.

Preparation Example 8 Preparation of Polyvinyl Acetate Nanofiber Nonwoven Fabric Containing Functional Natural Extract

A polyvinyl acetate nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Preparation Example 1, except that the electrospinning voltage was adjusted to 15 kV.

Preparation Example 9 Preparation of Functional Natural Extract Polyvinyl Acetate Nano Fiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 4 wt.%.

Preparation Example 10 Preparation of Functional Natural Extract Polyvinyl Acetate Nano Fiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 5 wt.%.

Preparation Example 11 Preparation of Functional Natural Extract Polyvinyl Acetate Nano Fiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 6 wt.%.

Preparation Example 12 Preparation of Polyvinyl Acetate Nanofiber Nonwoven Fabric Containing Functional Natural Extract

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 7 wt.%.

Preparation Example 13 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 8 wt.%.

Preparation Example 14 Preparation of Functional Natural Extract Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl acetate nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Preparation Example 8 except that the concentration of polyvinyl acetate was adjusted to 9 wt.%.

The conditions and results of Preparation Examples 1 to 14 were collectively shown in Table 1 below.

division	Used polymer	Polymer concentration	Natural Extract Concentration	Voltage	Distance between Tip and Collector
Preparation Example 1	Polyvinyl Acetate (PVAc)	3 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 2	Polyvinyl Acetate (PVAc)	4 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 3	Polyvinyl Acetate (PVAc)	5 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 4	Polyvinyl Acetate (PVAc)	6 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 5	Polyvinyl Acetate (PVAc)	7 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 6	Polyvinyl Acetate (PVAc)	8 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 7	Polyvinyl Acetate (PVAc)	9 wt.%	1 wt.%	17.5 kV	10 cm
Preparation Example 8	Polyvinyl Acetate (PVAc)	3 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 9	Polyvinyl Acetate (PVAc)	4 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 10	Polyvinyl Acetate (PVAc)	5 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 11	Polyvinyl Acetate (PVAc)	6 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 12	Polyvinyl Acetate (PVAc)	7 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 13	Polyvinyl Acetate (PVAc)	8 wt.%	1 wt.%	15 kV	10 cm
Preparation Example 14	Polyvinyl Acetate (PVAc)	9 wt.%	1 wt.%	15 kV	10 cm

In Examples 1 to 14, the functional natural extract-containing polyvinyl acetate nanofiber nonwoven fabric prepared in Preparation Example 1 was saponified to prepare an experiment to prepare a functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric. The polyvinyl acetate nanofiber nonwoven fabric containing the functional natural extract prepared in Preparation Example 1 was added to a nanofiber nonwoven fabric subjected to saponification using an alkali solution in distilled water, stirred again, and then dried at room temperature, followed by polyvinyl alcohol nano containing the functional natural extract. Fibrous nonwovens were prepared.

Example 1: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

For saponification of the functional natural extract-containing polyvinyl acetate nanofiber nonwoven fabric prepared by electrospinning, based on 1 g of the functional natural extract-containing polyvinyl acetate nanofiber nonwoven fabric, distilled water (100 mL), NaOH (10 g), Na _An alkaline solution was prepared by gently stirring ₂ SO ₄ (10 g), MeOH (10 g). A functional natural extract-containing polyacetic acid nanofiber nonwoven fabric was added to the prepared alkaline solution, and the saponification reaction was performed at 40 ° C. for 1 hour. After the saponification reaction, the nanofiber nonwoven fabric was washed several times with distilled water, and the washed nanofiber nonwoven fabric was dried at room temperature for 12 hours to prepare a polyvinyl alcohol nanofiber nonwoven fabric containing saponified functional natural extract.

Example 2: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 1 except that the saponification reaction time was adjusted to 2 hours.

Example 3: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 1 except that the saponification reaction time was adjusted to 3 hours.

Example 4: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 1 except that the saponification reaction time was adjusted to 6 hours.

Example 5: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing a functional natural extract was prepared in the same manner as in Example 1 except that the saponification reaction temperature was adjusted to 30 ° C.

Example 6: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 5 except that the saponification reaction time was adjusted to 2 hours.

Example 7: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric was prepared in the same manner as in Example 5 except that the saponification reaction time was adjusted to 3 hours.

Example 8: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 5 except that the saponification reaction time was adjusted to 6 hours.

Example 9: Preparation of functional natural extracts containing polyvinyl acetate nanofibers functional natural extract containing a polyvinyl alcohol nanofiber non-woven fabric by non-woven fabric non-homogeneous saponification of

Containing functional natural extract in the same manner as in Example 1 except for using an alkaline solution prepared with distilled water (50 mL), NaOH (5 g), Na ₂ SO ₄ (5 g), MeOH (5 g) Polyvinyl alcohol nanofiber nonwoven fabric was prepared.

Example 10 Preparation of Functional Natural Extract-Containing Polyvinyl Alcohol Nanofiber Nonwoven Fabrics through Heterogeneous Saponification of Functional Natural Extract-Containing Polyvinyl Acetate Nanofiber Nonwoven Fabrics

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 9 except that the saponification reaction time was adjusted to 2 hours.

Example 11 Preparation of Functional Natural Extract-Containing Polyvinyl Alcohol Nanofiber Nonwoven Fabric through Heterogeneous Saponification of Functional Natural Extract-Containing Polyvinyl Acetate Nanofiber Nonwoven Fabric

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 9 except that the saponification reaction time was adjusted to 3 hours.

Example 12 Preparation of Functional Natural Extract-Containing Polyvinyl Alcohol Nanofiber Nonwoven Fabrics through Heterogeneous Saponification of Functional Natural Extract-Containing Polyvinyl Acetate Nanofiber Nonwoven Fabrics

A polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract was prepared in the same manner as in Example 9 except that the saponification reaction time was adjusted to 6 hours.

The conditions and results of Examples 1 to 12 are summarized in Table 2 below.

division	Distilled water	Alkaline solution			Temperature	Saponification reaction time
		NaOH	Na 2 SO 4	MeOH
Example 1	100 mL	10 g	10 g	10 g	40 ℃	1 hours
Example 2	100 mL	10 g	10 g	10 g	40 ℃	2 hours
Example 3	100 mL	10 g	10 g	10 g	40 ℃	3 hours
Example 4	100 mL	10 g	10 g	10 g	40 ℃	6 hours
Example 5	100 mL	10 g	10 g	10 g	30 ℃	1 hours
Example 6	100 mL	10 g	10 g	10 g	30 ℃	2 hours
Example 7	100 mL	10 g	10 g	10 g	30 ℃	3 hours
Example 8	100 mL	10 g	10 g	10 g	30 ℃	6 hours
Example 9	50 mL	5 g	5 g	5 g	40 ℃	1 hours
Example 10	50 mL	5 g	5 g	5 g	40 ℃	2 hours
Example 11	50 mL	5 g	5 g	5 g	40 ℃	3 hours
Example 12	50 mL	5 g	5 g	5 g	40 ℃	6 hours

Through the above experiment, 50 to 100 mL of distilled water, 5 to 10 g of NaOH, 5 to 10 g of Na ₂ SO _{4, and} 5 to 10 g of MeOH were added to an alkali solution containing a temperature of 30 to 40 ° C. and a saponification time of 1 to In the case of the natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric prepared by the step of heterogeneous saponification by 6 hours, it was confirmed that the natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric having a saponification degree of 60% to 99.9% was formed. In particular, prepared by the step of the non-uniform saponification containing a functional natural extract by adding to an alkaline solution containing 100 mL of distilled water, 10 g of NaOH, 10 g of Na ₂ SO _4, 10 g of MeOH by temperature 40 ℃, saponification time 3 hours. In the case of the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric, it was confirmed that the natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric having a saponification degree of 99.9% was formed.

As an experimental example to support the effect of the present invention, Experimental Example 1 relates to the surface morphology analysis of the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric, Experimental Example 2 is the functionality of the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric It's about analysis. More specifically, it is shown in Experimental Examples 1 to 2 below.

Experimental Example 1 Surface Morphology Analysis of Polyvinyl Alcohol Nanofiber Nonwoven Fabric Containing Functional Natural Extracts

The surface morphology of the polyvinyl alcohol nanofiber nonwoven fabric containing the functional natural extract according to the alkali solution amount and saponification time was analyzed. The results are shown in FIGS. 3 and 4.

3 is a scanning electron micrograph of a non-uniform saponified functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric prepared according to an alkali solution amount. The temperature is the same at 40 ° C saponification time 3 hours.

(a) NaOH (5 g), Na ₂ SO ₄ (5 g), MeOH (5 g)

(b) NaOH (10 g), Na ₂ SO ₄ (10 g), MeOH (10 g)

4 is a scanning electron micrograph of a non-uniform saponified functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric prepared according to saponification time. Alkaline solution required for saponification is the same with NaOH (10 g), Na ₂ SO ₄ (10 g), MeOH (10 g), temperature 40 ℃.

(a) 1 hour saponification time

(b) saponification time 6 hours

3 and 4, it is confirmed that the uneven wrinkles on the surface of the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric of the present invention are not directional but folded in a large number, thereby maximizing the specific surface area of the nanofiber nonwoven fabric. Can be.

Experimental Example 2: Functional analysis of polyvinyl alcohol nanofiber nonwoven fabric containing functional natural extract

FIG. 5 is a view showing the results of a patch test for skin safety evaluation by applying the prepared functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric to the skin, and FIG. 6 is a table showing criteria for judging the international contact dermatitis study group. .

As the functional natural extracts were used as described above Fukryeong and sorghum extract, and the patch test was carried out using the functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric prepared in Example 1.

5 and 6, as a result of the patch test, it was confirmed that no trouble with the skin did not occur and contact dermatitis was not induced. The patch test was carried out using a Finn chamber on scanpor tape on the skin of the arm using a polyvinyl alcohol nanofiber nonwoven fabric (b) and a polyvinyl alcohol nanofiber nonwoven fabric (a) containing functional natural extracts stored at room temperature for 2 weeks. The skin reaction is visually confirmed after 24 hours of closed patching, and the criteria for evaluation are based on the judgment of the International Contact Dermatitis Study Group.

When the polyvinyl alcohol nanofiber nonwoven fabric (a), a nanofiber nonwoven fabric hermetically sealed for 24 hours, is patched with air, the air does not circulate and erythema appears on the skin, while polyvinyl alcohol nanofibers containing Fukryeong and sorghum extracts When the non-woven fabric (b) is patched, there are many wrinkles, and erythema does not appear because the functional (antibacterial and antioxidant properties) by Bokyeong and sorghum extract are given to the surface in contact with the skin.

7 is a scanning electron micrograph of the prepared non-uniform saponified polyvinyl alcohol nanofiber nonwoven fabric. Referring to Figure 7, it can be seen that the diameter of the fiber is formed in the size range of 80 nm to 2,000 nm under the condition of 13 wt.% Concentration.

Claims (18)

1. Converting the functional extract-containing polyvinyl acetate nanofiber nonwoven into a functional extract-containing polyvinyl alcohol nanofiber nonwoven in a state where the functional extract-containing polyvinyl acetate nanofiber nonwoven is impregnated in a first solvent capable of maintaining the nonwoven form A method of producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric comprising a wrinkle and nano pores formed on the surface.
2. The polyvinyl alcohol nanofiber of claim 1, wherein the functional extract-containing polyvinyl acetate nanofiber nonwoven fabric is prepared by electrospinning a functional extract and a spinning solution in which polyvinyl acetate is dissolved in a second solvent. Method for manufacturing nonwoven fabrics.
3. According to claim 2, wherein the functional extract is a method of producing a functional extract-containing polyvinyl alcohol film, using the same solvent as the extraction solvent of the second solvent.
4. The method of claim 2, wherein the functional extract is Fukryeong, sorghum, Eoseongcho, Doin, Doinpi, Panrameungi, Rigida, Sichuan, mantle mushroom, cloud fingering, Ganoderma lucidum, Sinyihwa, pogongyoung, Yulpi, camellia oil, phytoncide, willow, Birch, pine, elm, meadowsweet, purple, potato, licorice, red ginseng, brown alga, guar gum, oyster, grape seed, honey, green tea, carrot, sugar, camellia oil, wild chrysanthemum, strawberry, rosemary, locust bean gum, maca Damian Nut Oil, Matricaria, Starch, Bifidus, Saffron Oil, Morus, Sage, Loofah, Vegetable Squalane, Silk, Acacia, Rice, Mugwort, Almond, Avocado, Ivy, Aloe, Corn, Olive, Milk Protein, Turmeric, oil-soluble licorice, ginseng, peony, rose, iris, horoscope, gardenia, coconut, parsley, henna, hostile, jojoba, ocher, natural organic sulfur, grape seed, pomegranate, beta carotene, vitamin, herb, ginger, branch, zigolpi , Pansymus, soybean, lotus leaf A method for producing a functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric, characterized in that the extract, a mixture thereof or one or more thereof.
5. The method of claim 2, wherein the second solvent is methanol, ethanol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, ethyl acetate, methylene chloride, methyl ethyl ketone, toluene, ethylene glycol di A method of producing a functional natural extract-containing polyvinyl alcohol nanofiber nonwoven fabric, characterized in that it is an acetate or a mixed solvent thereof.
6. The method according to claim 2, wherein the concentration of polyvinyl acetate in the spinning solution is 1 wt.% To 30 wt.%.
7. According to claim 2, The electrospinning is characterized in that the distance between the capillary tube and the integrated plate to 1 cm to 30 cm, it is carried out under the conditions of the applied voltage 5 kV to 40 kV, functional extract-containing polyvinyl alcohol nano Method for producing fibrous nonwovens.
8. The method of claim 1, wherein the first solvent is an acid solution or an alkaline solution, including a dispersant and a swelling agent.
9. The method of claim 8, wherein the dispersing agent is sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or a mixture thereof.
10. The swelling agent of claim 8, wherein the swelling agent is methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, or a mixture thereof. Method for producing polyvinyl alcohol nanofiber nonwoven fabric containing extract.
11. The method of claim 8, wherein the acid solution is hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof; Any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, or mixtures thereof; And a method of producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric, which is prepared by mixing water.
12. The method of claim 8, wherein the alkaline solution is sodium chloride, sodium hydroxide, potassium hydroxide, sodium bromide, sodium iodide or mixtures thereof; Any one dispersant selected from sodium sulfate, sodium sulfite, calcium sulfate, magnesium sulfate, or mixtures thereof; Any one of swelling agents selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, acetone, or mixtures thereof; And a method of producing a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric, which is prepared by mixing water.
13. The method of claim 8, wherein the first solvent is sodium chloride; Sodium sulfate; Methanol; And an alkaline solution in which water is mixed and dissolved to prepare a functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric.
14. The method of claim 1, wherein the saponification step is performed for 1 hour to 6 hours at a temperature range of 5 ℃ to 80 ℃, a method for producing a polyvinyl alcohol nano fiber nonwoven fabric containing a functional extract.
15. A polyvinyl alcohol nanofiber nonwoven fabric containing functional extracts having wrinkles formed on the surface thereof and having nanopores having a porosity of 50% to 95%, prepared by the method of any one of claims 1 to 14.
16. 16. The polyvinyl alcohol nanofiber nonwoven fabric of claim 15, wherein the depth of the pleats of the polyvinyl alcohol nanofiber nonwoven fabric is 10 nm to 10 µm.
17. The method of claim 15, wherein the functional natural extract is Bokryeong, sorghum, Eoseongcho, Doin, Doinpi, Panrameungi, Rigida, Sichuan, mantle mushroom, cloud fingerling, Ganoderma lucidum, Sinyihwa, Pogongyoung, Yulpi, camellia oil, phytoncide, willow , Birch, pine, elm, meadowsweet, alder, potato, licorice, red ginseng, brown seaweed, guar gum, oyster, grape seed, honey, green tea, carrot, sugar, camellia oil, wild chrysanthemum, strawberry, rosemary, locust bean gum, Macadamia Nut Oil, Matricaria, Starch, Bifidus, Saffron Oil, Morus, Sage, Scrubber, Vegetable Squalane, Silk, Acacia, Rice, Mugwort, Almond, Avocado, Ivy, Aloe, Corn, Olive, Milk Protein , Turmeric, oil-soluble licorice, ginseng, peony, rose, iris, horoscope, gardenia, coconut, parsley, henna, hostile, jojoba, ocher, natural organic sulfur, grape seed, pomegranate, beta carotene, vitamin, herb, ginger, branch, Phalanx, Panlamus, A functional extract-containing polyvinyl alcohol nanofiber nonwoven fabric, characterized in that the lotus leaf extract, and a composite or a mixture thereof.
18. The polyvinyl alcohol nanofiber nonwoven fabric of claim 15, wherein the concentration of the functional extract is 0.05 wt.% To 10 wt.%.

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