WO2016171331A1 - Mask pack comprising nanofibers - Google Patents

Abstract

The present invention relates to mask pack comprising nanofibers and a method for manufacturing the same, the mask pack comprising a substrate and a nanofiber layer. The present invention is advantageous in that adhesion between a substrate layer and a polymer electrospun layer is easy, no detachment occurs, existence of the nanofiber layer substantially improves the skin attachment property, the same has a high ratio of impregnation with moisture-retaining components and various nutrients, and the same exhibits an excellent effect of diffusion through skin.

Description

[Revision according to Rule 26 04.08.2015] Mask pack containing nano fiber

The present invention relates to a mask pack including nanofibers, and more particularly to a mask pack containing heterogeneous nanofibers and nanofibers of different diameters.

A mask pack is a cosmetic that cleans and beautifulens the skin and restores the skin's physiological function by covering the skin such as the face and supplying moisture and beauty ingredients to the skin. Such a mask pack is prepared by impregnating a variety of nutrients good for skin care in synthetic fibers such as non-woven fabrics, as disclosed in Patent Publication No. 10-2011-0122473, and exerts a skin care effect by using a certain time attached to the face.

In general, a conventional mask pack manufacturing method is to fold the face-shaped non-woven fabric or the corresponding backing film with the non-woven fabric by hand, and to fold them manually by inserting the packaging material, filling the contents, suture and commercialize. At this time, the nonwoven fabric used has a disadvantage that the thickness is thick (15-50), the surface area per volume is small, and even a slight facial movement may fall off the facial skin tissue. In addition, there is a problem that the long-lasting effect of the cosmetic liquid after adhesion is also lowered.

In order to solve the above problem, Japanese Patent Application Laid-Open No. 2007-70347 discloses a skin pack mask pack including a nanofiber layer. However, the nanofiber-coated nonwoven mask pack has a possibility that delamination may occur when impregnated with a liquid cosmetic formulation because the adhesion between the nanofiber and the nonwoven fabric is only dependent on the electrostatic force. Is the reality.

In addition, as the electrospinning to form the nanofiber layer was performed at room temperature, the diluent had to be used excessively in order to maintain a constant viscosity of the polymer solution. Too much use of the diluent reduces the concentration of the polymer solution, which decreases the efficiency of electrospinning and causes a problem of environmental pollution.

Recently, a nanofiber layer is used a lot to manufacture a mask pack. The use of the nanofiber layer greatly improves skin adhesion, impregnation efficiency of moisturizing ingredients and various nutrients, and can provide a mask pack with excellent diffusion effect of nutrients through the skin.

The nanofiber layer is formed through electrospinning to contain the skin moisturizing component and nutrients as much as possible. Conventional electrospinning places a certain number of nozzles in a particular direction within the unit for electrospinning and radiates at a constant speed and time to the front of the substrate.

Conventional electrospinning devices are formed by laminating a nanofiber layer on a substrate by electrospinning a specific polymer solution under appropriate conditions due to the configuration of a unit for electrospinning and a nozzle and a nozzle block installed in the unit.

At this time, the nanofibrous layer laminated on the substrate by electrospinning is more effective in filtering foreign matters if the concentration of the polymer solution per unit area, that is, the basis weight, is different depending on the concentration of the pollutants and the degree of generation of the foreign matters. However, in the conventional nanofiber filter, since the polymer solution was uniformly electrospun in forming the nanofiber layer, the polymer solution was inevitably used, and thus the production cost was inevitably increased. In addition, there was an inevitable problem of environmental pollution caused by the use of an excess solvent.

However, there has not been any report on a device for manufacturing a mask pack using a polymer nanofiber layer having a different basis weight in manufacturing a mask pack.

The present invention has been made to solve the above problems, and a main object of the present invention is to provide a mask pack comprising a substrate (substrate) and nanofiber layer.

According to a suitable embodiment of the present invention for solving the above problems, there is provided a base material; A first nanofiber layer formed by electrospinning a polyacrylonitrile solution; A second nanofiber layer laminated on the first nanofiber layer by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and hydrophobic polyurethane; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided an article comprising: a substrate; A first nanofiber layer formed by electrospinning a polyvinyl alcohol solution; A second nanofiber layer laminated on the first nanofiber layer by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and hydrophobic polyurethane; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided a polyethylene terephthalate substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the polyethylene terephthalate substrate; It provides a mask pack comprising a.

According to a preferred embodiment of the present invention, there is provided a cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the cellulose base; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided a polyethylene terephthalate substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane attached to the other side of the polyethylene terephthalate substrate; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided a cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane attached to the other side of the cellulose base; It provides a mask pack comprising a.

According to a suitable embodiment of the present invention, there is provided a polyethylene terephthalate substrate; A first nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the polyethylene terephthalate substrate; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided a cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the cellulose base; It provides a mask pack comprising a.

According to another suitable embodiment of the present invention, there is provided an article comprising: a substrate; A first nanofiber layer formed by electrospinning a polyurethane solution; A second nanofiber layer formed by laminating a polyvinylidene fluoride solution on the first nanofiber layer; It provides a mask pack comprising a.

According to a suitable embodiment of the present invention, there is provided a base material comprising: a substrate; A first nanofiber layer having a diameter of 80 to 150 nm formed by electrospinning polyvinylidene fluoride; A second nanofiber layer having a diameter of 150 to 300 nm formed by electrospinning polyvinylidene fluoride; It provides a mask pack comprising a.

      According to another suitable embodiment of the present invention, there is provided an article comprising: a substrate; A first nanofiber layer having a diameter of 80 to 150 nm formed by electrospinning polyurethane; A second nanofiber layer having a diameter of 150 to 300 nm formed by electrospinning polyurethane; It provides a mask pack comprising a.

At this time, the adhesion between the substrate and the nanofiber layer is characterized in that the adhesive is formed through the adhesive layer formed by electrospinning the low melting polymer solution, the low melting polymer solution is a low melting point polyester, low melting point polyurethane, low melting point poly It is characterized in that at least one member selected from the group consisting of vinylene fluoride, the low melting polymer solution is characterized in that the electrospinning on the front surface or a portion of the substrate or nanofiber layer.

In addition, the nanofiber layer is characterized in that it is formed by electrospinning at a temperature of 50 to 100 ℃, the nanofiber layer is characterized in that the basis weight is different in the longitudinal or transverse direction, the polymer for forming the nanofiber layer The solution is characterized in that the viscosity is maintained at 1,000 cps to 3,000 cps through a thermostat.

The manufacturing method of the filter according to the present invention is partitioned into at least two spinning sections, and through each spinning section to obtain a filter which is formed by stacking two or more layers by electrospinning different polymers continuously, thereby producing a filter. It can be simplified and simplified, which has the economic advantage of reducing the manufacturing cost and manufacturing time.

1 is a side view schematically showing an electrospinning device according to the present invention;

Figure 2 is a side cross-sectional view schematically showing a nozzle of a nozzle block installed in each unit of the electrospinning apparatus according to the present invention;

Figure 3 is a side cross-sectional view schematically showing another embodiment according to the nozzle of the nozzle block installed in each unit of the electrospinning apparatus according to the present invention;

Figure 4 is a nozzle block installed in each unit of the electrospinning apparatus according to the present invention

Schematic floor plan,

5 is a front sectional view schematically showing a state in which a heat transfer apparatus is installed in a nozzle block installed in each unit of an electrospinning apparatus according to the present invention;

6 is a cross-sectional view taken along line AA ′ of FIG. 5;

Figure 7 is a front sectional view schematically showing another embodiment of the state in which the heat transfer apparatus is installed in the nozzle block installed in each unit of the electrospinning apparatus according to the present invention;

8 is a cross-sectional view taken along the line B-B 'of FIG.

9 is a front sectional view schematically showing still another embodiment of a state in which a heating apparatus is installed in a nozzle block installed in each unit of an electrospinning apparatus according to the present invention;

10 is a cross-sectional view taken along the line C-C 'of FIG.

11 is a view schematically showing an auxiliary transport device of an electrospinning apparatus according to the present invention;

12 is a view schematically showing another embodiment of the auxiliary belt roller of the auxiliary transport device of the electrospinning apparatus according to the present invention,

13 to 16 is a side view schematically showing the operation of the long sheet feed rate adjusting apparatus of the electrospinning apparatus according to the present invention;

17 is a side view schematically showing an electrospinning device for manufacturing a filter including an adhesive layer according to the present invention;

18 is a perspective view schematically showing a nozzle block installed in an adhesive (low melting point polymer) unit of an electrospinning apparatus according to the present invention;

19 is a plan view schematically illustrating a nozzle block installed in an adhesive (low melting point polymer) unit of an electrospinning apparatus according to the present invention;

20 to 21 are installed in each unit of the electrospinning apparatus according to the present invention

A plan view schematically illustrating an operation process of sequentially spraying the adhesive (low melting point polymer) and the polymer spinning solution through the nozzle block,

22 is a plan view schematically showing another embodiment according to the nozzle tube arranged in the nozzle block of the electrospinning apparatus according to the present invention;

FIG. 23 is a front view of FIG. 22;

24 is a side view schematically showing another embodiment according to the nozzle tube arranged in the nozzle block of the electrospinning apparatus according to the present invention;

25 and 26 are through the nozzle of each nozzle pipe of the electrospinning apparatus according to the present invention.

And the polymer spinning solution is electrospun on the same plane of the substrate (the nozzle indicated by the broken line in FIG. 25 is closed, and the nozzle indicated by the broken line in FIG. 26 indicates that it is located under the substrate). Plan view schematically showing an embodiment,

27 is a plan view schematically showing still another embodiment according to the nozzle tube which is arranged in the nozzle block of the electrospinning apparatus according to the present invention;

28 is a perspective view schematically showing still another embodiment according to the nozzle tube arranged in the nozzle block of the electrospinning apparatus according to the present invention;

29 and 30 are through the nozzle of each nozzle pipe of the electrospinning apparatus according to the present invention.

Plan view schematically showing another embodiment according to the operation process by which the polymer spinning solution is electrospun on the same plane of the substrate,

31 and 32 are schematic diagrams showing a filter including a nanofiber layer of the present invention,

33 is a side view schematically showing an electrospinning device according to the present invention;

34 is a perspective view schematically showing a flip device of an electrospinning device according to the present invention;

35 to 38 schematically show the operation of the flip device of the electrospinning apparatus according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.

According to one embodiment of the invention, the first nanofiber layer formed by electrospinning the first polymer solution on the substrate; The present invention provides a mask pack including a second nanofiber layer formed by stacking a second polymer solution on the first nanofiber layer by electrospinning a solution.

Here, according to a preferred embodiment of the present invention, the first polymer solution is polyurethane, and the second polymer solution is polyvinylidene fluoride.

According to another suitable embodiment of the present invention, the first polymer solution is polyvinyl alcohol or polyacrylonitrile, and the second polymer solution is hydrophobic polymer.

On the other hand, according to another embodiment of the present invention, the present invention is formed by electrospinning a polyvinylidene fluoride solution on a substrate, the first nano-fibers made of polyvinylidene fluoride nanofibers having a fiber diameter of 80 to 150nm Fibrous layer; The present invention provides a mask pack including a second nanofiber layer formed by laminating a polyvinylidene fluoride solution on the first nanofiber layer, and having a polyvinylidene fluoride nanofiber having a fiber diameter of 150 to 300 nm.

In addition, according to another embodiment of the present invention, the present invention is formed by electrospinning a polyurethane solution on a substrate, the first nanofiber layer made of polyurethane nanofibers having a fiber diameter of 80 to 150nm; The present invention provides a mask pack including a second nanofibrous layer formed of polyurethane nanofibers having a fiber diameter of 150 to 300 nm by being laminated by electrospinning a polyurethane solution on the first nanofiber layer.

On the other hand, according to an embodiment of the present invention, the present invention comprises a first nanofiber layer formed by electrospinning the first polymer solution on one side of the substrate; It provides a mask pack comprising a; the second nanofiber layer formed by electrospinning the second polymer solution on the other side of the substrate.

Here, the substrate is a polyethylene terephthalate substrate or a cellulose substrate, wherein the first polymer solution and the second polymer solution is characterized in that the hydrophilic polymer or hydrophobic polymer.

In this case, the hydrophilic polymer used in the present invention is preferably one selected from the group consisting of polyethersulfone, polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane, but is not limited thereto.

In addition, the hydrophobic polymer used in the present invention is preferably one selected from the group consisting of polyvinylidene fluoride, low melting polyester and hydrophobic polyurethane, but is not limited thereto.

At this time, the filter is characterized in that it is manufactured using an electrospinning device.

The polyvinylidene fluoride (PVDF) -based polymer electrolyte used according to the preferred embodiment of the present invention is prepared by preparing a polymer matrix to have a porosity of submicron or less, and then injecting an organic electrolyte solution into these small pores. The compatibility with the electrolyte is excellent, the organic electrolyte in the small pores has the advantage that can be used as a safe electrolyte without leakage, and since the organic solvent electrolyte is injected later, the polymer matrix can be produced in the air.

In addition, the weight average molecular weight (Mw) of the said polyvinylidene fluoride resin is although it does not specifically limit, It is preferable that it is 10,000-500,000, and it is more preferable that it is 50,000-500,000. When the weight average molecular weight of the polyvinylidene fluoride resin is less than 10,000, the nanofibers constituting the nanofibers may not obtain sufficient strength, and when the polyvinylidene fluoride resin exceeds 500,000, the solution may not be easily handled and the processability may be poor, resulting in uniform nanofibers. It becomes difficult to obtain.

The low-melting polyester used in accordance with another suitable embodiment of the present invention is preferably a hydrophobic polymer, using terephthalic acid, isophthalic acid and mixtures thereof. In order to further lower the melting point, ethylene glycol may be added as the diol component.

Hydrophobic polyurethanes used according to another suitable embodiment of the present invention have a calcined branched structure, which reacts polyalkylene oxides with polyfunctional materials, diisocyanates and water, and the resulting product is subjected to hydrophobic coherent activity. It can be prepared by end capping with a hydrogen containing compound or mono isocyanate. Hydrophobic groups can be independently selected from the group consisting of alkyl, aryl, arylalkyl, alkenyl, arylalkenyl, alicyclic, perfluoroalkyl, carbosilyl, polycyclyl and composite resins, wherein alkyl, al Kenyl, perfluoroalkyl and carbosilyl hydrophobic groups contain 1-40 carbon atoms and aryl, arylalkyl, arylalkenyl, cycloaliphatic and polycyclyl hydrophobic groups contain 3-40 carbon atoms.

Polyacrylonitrile (PAN) used according to another suitable embodiment of the present invention means a polymer of acrylonitrile (CH2 = CHCN).

Scheme 1

Here, the polyacrylonitrile resin is a copolymer made from a mixture of acrylonitrile and units constituting most of them. Frequently used monomers include butadiene styrene vinylidene chloride or other vinyl compounds. Acrylic fibers contain at least 85% acrylonitrile and modacryl contains 35-85% acrylonitrile. When other monomers are included, the fiber has the property of increasing affinity for the dye. More specifically, in the production of acrylonitrile-based copolymers and spinning solutions, in the case of using acrylonitrile-based copolymers, nozzle contamination is less during the manufacturing of microfibers by the electrospinning method, and the electrospinning properties are excellent. By increasing the solubility in the solvent, it is possible to give better mechanical properties. In addition, polyacrylonitrile has a softening point of 300 ° C. or higher and excellent heat resistance.

In addition, the degree of polymerization of the polyacrylonitrile is 1,000 to 1,000,000, preferably 2,000 to 1,000,000.

And it is preferable to use polyacrylonitrile within the range which satisfy | fills the usage-amount of an acrylonitrile monomer, a hydrophobic monomer, and a hydrophilic monomer. The weight percent of acrylonitrile monomer during polymer polymerization is too low for electrospinning when the weight percentage of hydrophilic monomer and the weight percentage of hydrophobic monomer are less than 60 due to the ratio of 3: 4. Even if the crosslinking agent is added to the nozzle, it is difficult not only to cause nozzle contamination but also to form a stable jet during electrospinning. In addition, in the case of 99 or more, the spinning viscosity is too high, and spinning is difficult, and even if an additive is added to reduce the viscosity, the diameter of the ultrafine fibers becomes thick and the productivity of the electrospinning is too low to achieve the object of the present invention.

In addition, as the amount of the comonomer is increased in the acrylic polymer, the amount of the crosslinking agent should be added to ensure the stability of electrospinning and to prevent the mechanical properties of the nanofibers from deteriorating.

The hydrophobic monomer is used in ethylene-based compounds and derivatives thereof such as methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinylpyrrolidone, vinylidene chloride, and vinyl chloride. It is preferable to use any one or more selected.

The hydrophilic monomers are acrylic acid, allyl alcohol, metaallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, butene tricarboxylic acid, vinyl It is preferable to use any one or more selected from ethylene-based compounds such as sulfonic acid, allyl sulfonic acid, metalylsulfonic acid, parastyrene sulfonic acid, and polyhydric acids or derivatives thereof.

As an initiator used to prepare the acrylonitrile-based polymer, an azo compound or a sulfate compound may be used, but in general, it is preferable to use a radical initiator used for a redox reaction.

Polyvinylalcohol (PVA) used according to another suitable embodiment of the present invention is a biocompatible hydrophilic polymer material and can be used as a drug delivery system or membrane because of its excellent physical and mechanical properties and chemical resistance.

The polyvinyl alcohol has excellent biocompatibility, is easy to manufacture, has a swelling property, is suitable for absorbing the exudates of wounds, and has a -OH group to facilitate modification. The polyvinyl alcohol is currently applied to tissue regeneration of cartilage, breast augmentation, etc. in the form of hydrogel, and is composed of C, H, O, so that when the polymer is biodegraded, the decomposition product is not harmful to the human body, so it is less toxic. In addition, the nanofiber-type membrane by the electrospinning method maintains the pores and is advantageous for angiogenesis, etc., and has excellent biocompatibility because it has a structure similar to the extracellular matrix.

Polyamide used according to another suitable embodiment of the present invention refers to a generic term for polymers linked by amide bonds (-CONH-), which can be obtained by condensation polymerization of diamines and divalent acids. Polyamides are characterized by amide bonds in their molecular structure and vary in physical properties depending on the proportion of amide groups. For example, when the ratio of amide groups in a molecule increases, specific gravity, melting point, water absorbency, rigidity, etc., are increased.

In addition, polyamide is a material that is applied in a wide range of fields such as clothing, tire cords, carpets, ropes, computer ribbons, parachutes, plastics, adhesives, etc. due to its excellent corrosion resistance, abrasion resistance, chemical resistance and insulation.

In general, polyamides are classified into aromatic polyamides and aliphatic polyamides. Typical aliphatic polyamides include nylon. Nylon is originally a trademark of DuPont, USA, but is currently used as a generic name.

Nylon is a hygroscopic polymer and reacts sensitively to temperature. Representative nylons include nylon 6, nylon 66 and nylon 46.

First, nylon 6 has excellent heat resistance, moldability, and chemical resistance properties, and is manufactured by ring-opening polymerization of ε-caprolactam to prepare it. Nylon 6 is because caprolactam has 6 carbon atoms.

Scheme 2

Nylon 66, on the other hand, is similar to nylon 6 in general, but has excellent heat resistance and superior self-extinguishing and abrasion resistance compared to nylon 6. Nylon 66 is prepared by dehydration condensation polymerization of hexamethylenediamine with adipic acid.

Scheme 3

In addition, nylon 46 is excellent in heat resistance, mechanical properties and impact resistance, processing temperature

Has a high advantage. Nylon 46 is made by polycondensation of tetramethylenediamine with adipic acid. Diaminobutane (DAB), a raw material, is prepared from the reaction between acrylonitrile and hydrogen cyanide.In the polymerization operation, a salt is prepared from diaminobutane and adipic acid in the first step, and then subjected to polymerization under an appropriate pressure. After conversion to a prepolymer, the solid of the prepolymer is prepared by polymerizing in a solid phase by treatment at about 250 ° C. in the presence of nitrogen and water vapor.

Nylon 46 in particular exhibits excellent characteristics with high amide concentrations and regular ordered arrangement between methylene and amide groups. The melting point of nylon 46 is about 295 ° C., which is higher than that of other types of nylon, and has attracted attention as a resin having excellent heat resistance due to the above characteristics.

Polyurethanes used in accordance with another suitable embodiment of the present invention may be prepared using known polyurethane reaction techniques. For example, an excess molar amount of organic diisocyanate is reacted with polyalkylene ether glycol in an amide polar solvent to prepare an intermediate polymer having an isocyanate group at its terminal, and then the intermediate polymer is dissolved in an amide polar solvent and A polyurethane polymer can be obtained by making a terminal stop agent react.

In the preparation of the hydrophilic polyurethane prepolymer, the polyether polyols are preferably synthesized in a molar ratio of 0.15 to 0.95 to 1 to 3 moles of isocyanate.

Isocyanates include isophorone diisocyanate, 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, bis (2-isocyanate ether) -fumarate , 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,6-hexanediisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethylphenylene diisocyanate, p-phenyl Rendiisocyanate, m-phenylenediisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate and the like can be used, preferably diphenylmethane diisocyanate, 2,4 Toluene diisocyanate and isomers thereof, p-phenylenedi isocyanate, isophorone diisocyanate, hexamethylene diisocyanadi It is better to use the network.

The polyether polyols have an ethylene oxide / propylene oxide random copolymer having three or more hydroxyl groups in a molecule having a molecular weight of 3,000 to 6,000 and an ethylene oxide content of 50 to 80%, and a molecular weight of 1,000 to Ethylene oxide / propylene oxide random copolymer having a molecular weight of 3,000 to 6,000 and an ethylene oxide content of 50 to 80%, having three hydroxyl groups in the molecule, and preferably used in a mixture of 30:70 to the weight of 4,000 polypropylene glycol. It is better to use alone. However, other isocyanate compounds and polyols not mentioned above may be mixed for controlling physical properties.

It is preferable that the heat resistant polymer used according to another suitable embodiment of the present invention is one kind of polymer selected from the group consisting of polyimide, metaaramid and polyethersulfone.

Meanwhile, the polyimide, which is one of the heat resistant polymers used in the present invention, may be prepared by a two step reaction.

The first step is to prepare a polyamic acid, as shown in Scheme 1 below,

The polyamic acid proceeds by adding dianhydride to a reaction solution in which diamine is dissolved, and in order to increase the degree of polymerization, the reaction temperature, the moisture content of the solvent, and the purity of the monomer are required.

Scheme 4

As the solvent used in the first step, organic polar solvents of dimethylacetamide (DMAc), dimethylformamide (DMF) and en-methyl-2-pyrrolidone (NMP) are mainly used. The anhydrides include pyromellyrtic dianhydride (PMDA), benzophenonetetracarboxylic hydride (BTDA), 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride, ODPA), biphenyltetracarboxylic dianhydride (BPDA) and bis (3,4'-dicarboxyphenyl) dimethylsilanedihydride (bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA) It can be used to include one.

Further, the diamine may be 4,4'-oxydianiline (4,4'-oxydianiline, ODA), paraphenylenediamine (p-penylene diamine, p-PDA) and orthophenylenediamine (o-penylenediamine, o-PDA) may be used.

Thereafter, as shown in Scheme 2 below, the following four methods are representative as a second step of dehydration and ring-closure reaction for preparing a polyimide from the polyamic acid prepared in the first step.

Scheme 5

First, the reprecipitation method adds a polyamic acid solution to the excess solvent (Poor solvent)

As a method of obtaining a solid polyamic acid, although water is mainly used as a reprecipitation solvent, toluene, ether, etc. can be used as a cosolvent.

Chemical imidization is a method of chemically imidizing a reaction using a dehydration catalyst such as acetic anhydride / pyridine, and is useful for preparing a polyimide film.

The thermal imidization method is a method of thermally imidating a polyamic acid solution by heating it to 150-200 ° C. The simplest process or crystallinity is high, and the polymer is decomposed because an amine exchange reaction occurs when an amine solvent is used. There is this.

Isocyanate method uses diisocyanate as monomer instead of diamine.

When the monomer mixture is heated to a temperature of 120 ° C. or more, a CO ₂ gas is generated and a polyimide is produced.

In addition, the specific gravity of metaaramid, which is one of the heat resistant polymers used in the present invention, is preferably 1.3 to 1.4, and preferably has a weight average molecular weight of 300,000 to 1,000,000. Most preferred weight average molecular weight is from 3,000 to 500,000.

The metaaramids include meta-oriented synthetic aromatic polyamides. Metaaramid polymers must have a fiber-forming molecular weight and can include polyamide homopolymers, copolymers, and mixtures thereof that are primarily aromatic, wherein at least 85% of the amide (-CONH-) bonds are directly directed to the two aromatic rings. Attached. The ring may be unsubstituted or substituted. The polymer becomes meta-aramid when two rings or radicals are meta-oriented relative to each other along the molecular chain. Preferably, the copolymer has up to 10% other diamines substituted with the primary diamine used to form the polymer, or up to 10% other diacids substituted with the primary diacid chloride used to form the polymer. Chloride. Preferred metaaramids are poly (meth-phenylene isophthalamide) (MPD-I) and copolymers thereof. One such metaaramid fiber is Lee. Wilmington, Delaware, USA. Child. Nomex® aramid fibers available from EI du Pont de Nemours and Company, while metaaramid fibers are available from Teijin Ltd., Tokyo, Japan. Trade name Tejinconex (registered trademark); New Star® meta-aramid, available from Yantai Spandex Co. Ltd, Shandong, China; And Chinfunex® Aramid 1313, available from Guangdong Charming Chemical Co. Ltd., Xinhui, Guangdong, China.

This meta-aramid is the first high heat-resistant aramid fiber, it can be used at 350 ℃ in a short time, 210 ℃ in continuous use, and when exposed to a temperature higher than this does not melt or burn like other fibers, it is carbonized . Above all, unlike other products that have been flame retardant or fireproof, it does not emit toxic gases or harmful substances even when carbonized and has excellent properties as an eco-friendly fiber.

In addition, since meta-aramid has a very strong molecular structure, the molecules constituting the fiber are not only strong in nature but also easily oriented in the fiber axial direction during the spinning step, thereby improving crystallinity and improving the strength of the fiber. There is an advantage to increase.

In addition, polyethersulfone (Polyethersulfone (PES)) is a amber transparent amorphous resin having the following repeating units, generally prepared by the polycondensation reaction of dichlorodiphenylsulfone.

Scheme 6

Polyethersulfone is a super heat-resistant engineering plastic developed by ICI, UK, and is a polymer having excellent heat resistance among thermoplastic plastics. Since polyethersulfone is amorphous, there is little physical property deterioration by temperature rise, and since the temperature dependence of flexural modulus is small, it hardly changes at -100-200 degreeC. Load distortion temperature is 200-220 degreeC, and glass transition temperature is 225 degreeC. In addition, the creep resistance up to 180 ° C. is the best among thermoplastic resins, and has the property of withstanding hot water or steam of 150 to 160 ° C.

Due to the above characteristics, polyether sulfone is used in optical discs, magnetic discs, electric and electronic fields, hydrothermal fields, automobile fields, and heat-resistant coatings.

Solvents usable with the polyethersulfone include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide (N, N-Dimethylformamide, DMF), dimethylacetamide (N, N-Dimethylacetamide, DMAc), N- Methyl-2-pyrrolidone (N-methyl pyrrolidone, NMP), cyclohexane, water, or mixtures thereof, and the like, but is not necessarily limited thereto.

Hereinafter, the electrospinning value used in the present invention will be described with reference to FIGS. 1 to 17.

1 is a side view schematically showing an electrospinning device according to the present invention, FIG. 2 is a side cross-sectional view schematically showing a nozzle of a nozzle block installed in each unit of an electrospinning apparatus according to the present invention, and FIG. Is a side cross-sectional view schematically showing another embodiment according to the nozzle of the nozzle block installed in each unit of the electrospinning apparatus according to the present invention, and FIG. 4 schematically shows a nozzle block installed in each unit of the electrospinning apparatus according to the present invention. FIG. 5 is a front sectional view schematically illustrating a state in which a heat transfer device is installed in a nozzle block installed in each unit of an electrospinning apparatus according to the present invention, and FIG. 6 is a cross-sectional view taken along line AA ′ of FIG. 5. 7 is a front end schematically showing another embodiment of the state in which the heat transfer device is installed in the nozzle block installed in each unit of the electrospinning apparatus according to the present invention. FIG. 8 is a cross-sectional view taken along line B-B 'of FIG. 7, and FIG. 9 schematically illustrates another embodiment of a heat transfer apparatus installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention. FIG. 10 is a cross-sectional view taken along line C-C 'of FIG. 9, and FIG. 11 is a view schematically showing an auxiliary transport apparatus of an electrospinning apparatus according to the present invention, and FIG. FIG. 13 is a view schematically showing another embodiment of the auxiliary belt roller of the auxiliary feeder, and FIGS. 13 to 16 are side views schematically showing an operation process of the long seat conveying speed adjusting device of the electrospinning device according to the present invention.

As shown in the figure, the electrospinning apparatus 1 according to the present invention comprises a bottom-up electrospinning apparatus 1, at least two or more units 10a, 10b are sequentially provided at regular intervals, and the Each unit 10a, 10b electrospins the same polymer spinning solution individually, or separately polymerizes the polymer spinning solution of different materials to produce a filter.

To this end, each unit (10a, 10b) is for supplying a fixed amount of the polymer spinning solution filled in the spinning solution main tank (8) and the spinning solution main tank (8) filled therein the polymer spinning solution therein Discharge the polymer spinning solution filled in the metering pump (not shown) and the spinning solution main tank (8), wherein the nozzle block 11 and the nozzle 12 are arranged in a plurality of nozzles (12) In order to accumulate the polymer spinning solution to be injected from the nozzle 12 is composed of a configuration comprising a collector 13 and a voltage generator (14a, 14b) for generating a voltage to the collector 13 spaced apart.

On the other hand, the electrospinning apparatus according to the present invention may be composed of four or more units, as shown in Figure 33, wherein the spinning solution unit 10b and the low melting point polymer unit 10c of the electrospinning apparatus 1 The top and bottom of the substrate passing through the spinning solution unit 10b are rotated by 180 ° by the flip device 110 provided therebetween. This will be described in detail as follows.

As shown in FIGS. 34 to 38, the low melting polymer unit 10a,

10b) is passed through the inner surface of the flip device 110, the substrate 15, the polymer spinning solution is electrospun on the bottom surface and the nanofiber layer is laminated to the rear end of the unit (10b) Each of them is formed inwardly and protrudes, and is rotated 180 ° while being transported along left and right guide members 111 and 111 'having guide grooves 112 and 112' for both ends of the substrate 15 to be inserted and guided. The upper and lower surfaces are reversed to the lower and upper positions.

At this time, any one of both ends of the substrate 15 is the inner circumference of the flip device 110

In the upward direction along the left guide member 111 of the guide members 111 and 111 'protruded inwardly.

After being transferred to the lower direction again and is transported in a position and direction opposite to the initial position, the other end of the substrate 15 is directed downward along the right guide member 111 '

After being transferred to the upper direction again and moved to the position and direction opposite to the initial position is inserted into each guide groove (112, 112 ') of the left and right guide member (111, 111').

The base 15 is rotated by 180 ° while being guided to the left and right guide members 111 and 111 '.

Each unit 10a, 10b, of the electrospinning apparatus 1 has the structure as described above.

The substrate 15 on which the nanofiber layer is laminated is rotated by 180 ° while the polymer spinning solution is electrospun on the lower surface while passing through the units 10a and 10b positioned at the tip side of the ends 10c and 10d.

As a result, the nanofiber layer may be formed by electrospinning the polymer spinning solution on the upper surface of the substrate 15 on which the polymer spinning solution is not electrospun during the passage of the units 10c and 10d positioned on the rear end side.

That is, the electric room by rotating the substrate 15 by 180 ° by the flip device 110

Nanofiber layer is laminated by electrospinning the polymer spinning solution on one side of the substrate 15 through the units 10a, 10b located at the tip side of each unit 10a, 10b, 10c, 10d of the yarn making machine 1. The substrate is formed by electrospinning a polymer spinning solution on the other side of the substrate 15 through the units 10c and 10d positioned at the rear end of each unit 10a, 10b, 10c, and 10d to form a nano-islet layer. The nanofiber layer may be laminated on both surfaces of (15).

That is, after passing through the spinning solution unit 10b, the substrate and the first poly laminated thereon

A fabric made of vinylidene fluoride nanofiber nonwoven is supplied to the flip device 110

In the flip device 110, the upper surface of the fabric is changed to a lower surface, and the lower surface of the fabric is rotated 180 degrees so that the position is changed to the upper surface.

By the structure as described above, the electrospinning apparatus 1 according to the present invention includes a plurality of nozzles 12 in which the polymer spinning solution filled in the spinning solution main tank 8 is formed in the nozzle block 11 through a metering pump. Continuously quantitatively supplied, the polymer spinning solution is supplied to the nanofiber on the long sheet (15) that is spun and concentrated on the collector 13 is subjected to a high voltage through the nozzle 12 is moved on the collector 13 The formed nanofibers are made into a filter.

Here, the front of the unit (10a) located at the front end of each unit (10a, 10b) of the electrospinning device (1) is supplied into the unit (10a) long to the nanofibers are laminated by the injection of the polymer spinning solution A feed roller 3 for supplying the sheet 15 is provided, and the long sheet 15 to which the nanofibers are laminated is formed on the rear of the unit 10c positioned at the rear end of each of the knits 10a and 10b. Winding roller 5 is provided.

Meanwhile, the long sheet 15 in which the polymer spinning solution is laminated while passing through the units 10a and 10b is preferably a release paper film, and the polymer spinning solution is spun onto the collector 13 without the long sheet 15. More preferably.

At this time, the material of the polymer spinning solution radiated through each unit (10a, 10b) of the electrospinning apparatus 1 is not limited separately, in the present invention, the unit (10a) is hydrophilic polymer, hydrophobic polymer, polyvinylidene One first polymer solution selected from the group consisting of fluoride and hydrophobic polyurethane is used, and unit 10b contains polyimide, metaaramid, polyethersulfone, polyvinylidene fluoride and hydrophobic polyurethane The selected second polymer solution is used, and the unit 10c is a third polymer solution selected from the group consisting of hydrophilic polymer, hydrophobic polymer, polyvinylidene fluoride and hydrophobic polyurethane. do.

In addition, the spinning solution supplied through the nozzle 12 in the units 10a and 10b is a solution in which the polymer of the electrospinable synthetic resin material is dissolved in a suitable solvent, and the type of solvent may also dissolve the polymer. But not limited to, for example, phenol, formic acid, sulfuric acid, m-cresol, thifluoroacetic & hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran Methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group m-butyl alcohol, isobutyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, aliphatic ketone group, propylene glycol as hexane, tetrachloroethylene, acetone, glycol group , Diethylene glycol, ethylene glycol, halogenated compounds, trichloroethylene, dichloromethane, aromatic compounds, toluene, xylene, aliphatic high Cyclohexanone, cyclohexane and ester groups as n-butyl acetate, ethyl acetate, aliphatic ether groups as butyl cellosalb, acetic acid 2-ethoxyethanol, 2-ethoxyethanol, amide dimethylformamide, Dimethyl acetamide, etc. can be used, A plurality of solvents can be mixed and used. It is preferable to contain additives, such as an electroconductivity improving agent, in a spinning solution.

On the other hand, the nozzle 12 provided in the nozzle block 11 of the electrospinning apparatus 1 according to the present invention, as shown in Figure 2, consists of a multi-tubular nozzle 500, two or more polymer chambers Two or more inner and outer tubes 501 and 502 are combined in a sheath-core shape to simultaneously electrospin the use liquid.

Here, the nozzle block 11 is located at the bottom of the nozzle plate 405 and the nozzle plate 405 in which the multi-tubular nozzle 500 is formed in a multi-pipe shape of a sheath-core type. And at least two spinning solution storage plates 407 and 408 for supplying a polymer spinning solution (not shown) to the multi-tubular nozzle 500 and an overflow removing nozzle 415 surrounding the multi-tubular nozzle 500 and the The overflow liquid temporary storage plate 410 and the overflow liquid temporary storage plate 410 which are connected to the overflow removing nozzle 415 and located directly above the nozzle plate 405 are located in the overflow portion. The overflow removal nozzle support plate 416 which supports the furnace removal nozzle 415 is comprised.

In addition, the air is positioned at the top of the air supply nozzle 404 and the nozzle block 11 surrounding the multi-tubular nozzle 500 and the overflow removing nozzle 415 to support the air supply nozzle 404. Located at the lower end of the support plate 414 of the supply nozzle and the support plate 414 of the air supply nozzle, the air inlet 413 for supplying air to the air supply nozzle 404 and the air storage for storing the supplied air The board 411 is comprised.

In addition, an overflow outlet 412 for discharging the overflow liquid to the outside through the overflow removal nozzle 415 is provided.

In one embodiment of the electrospinning apparatus 1 according to the present invention, the nozzle 12 is formed in a cylindrical shape, but as shown in FIG. 3, the nozzle 12 is formed in a wedge-shaped cylinder, The tip portion 503 is formed in the shape of a fallopian tube at an angle of 5 to 30 degrees to the axis.

Here, the tip portion 503 formed in the shape of the fallopian tube is formed in the form of narrowing from the top to the bottom, but if formed in the form of narrowing from the top to the bottom may be formed in various other shapes.

On the other hand, with reference to Figures 22 to 30 will be described in the nozzle tube 112 according to another embodiment of the present invention.

The nozzle block 111 of the electrospinning apparatus 100 has a plurality of nozzle pipes 112 arranged in the longitudinal direction thereof, and a spinning solution main tank 120 for supplying a polymer spinning solution to the nozzle pipes 112. At least one connection may be provided.

That is, the nozzle body (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is formed in a rectangular parallelepiped, a plurality of nozzles (111a) are provided linearly on the upper surface of the nozzle block 111 The nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are arranged in the longitudinal direction of the substrate 115 in a plurality, and are connected to the spinning solution main tank 120 Polymer spinning solution filled in the spinning solution main tank 120 is supplied.

Here, each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is connected to the spinning solution main tank 120 as a solution supply pipe 121, the solution supply pipe 121 is A plurality of branching bodies are connected to connect the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and the spinning solution main tank 120.

At this time, the supply amount adjusting means (not shown) to the solution supply pipe 121 that is addressed to each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) in the spinning solution main tank 120 Is provided, the supply amount adjusting means is made of a supply valve (122).

In this way, the supply valve 122 is provided in the solution supply pipe 121 which is extended from the spinning solution main tank 120 to each nozzle pipe 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i. The supply of the polymer spinning solution supplied from the spinning solution main tank 120 to each nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i by the respective supply valves 122 is controlled. And controlled by the controlled on-off system.

That is, the spinning solution when the polymer spinning solution is supplied from the spinning solution main tank 120 to each nozzle tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i through the solution supply pipe 121. The nozzle is opened and closed by the supply valve 122 provided in the solution supply pipe 121 extending the main tank 120 and the nozzle pipe bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i. It is optional only for the nozzle pipes 112b, 112d, 112f, 112g, 112h, 112i at a specific position among the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i arranged in the block 111. Each nozzle pipe 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning solution main tank 120 by opening and closing the supply valve 122, etc. The supply of the polymer spinning solution to be controlled is controlled.

To this end, the supply valve 122 is controllably connected to the control unit (not shown), it is preferable that the opening and closing of the supply valve 122 is automatically controlled by the control unit, according to the site situation and the needs of the operator It is also possible that the opening and closing of the supply valve 122 is controlled manually.

In one embodiment of the present invention, the supply amount adjusting means is composed of a supply valve 122, but in the spinning solution main tank 120, each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) Control and control of the supply amount of the polymer spinning solution to be supplied to the) If available, the supply amount adjusting means may be made of various other structures and means, but is not limited thereto.

By the structure as described above, the solution supply pipe 121 is to branch, while the spinning solution main tank 120 and each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) to be addressed Each of the supply valves 122 is provided in each of the plurality of nozzles 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i from the spinning solution main tank 120 to supply a plurality of polymer spinning solutions. A nozzle at a specific position among the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, which is installed in the nozzle block 111 by opening a specific supply valve 122 among the supply valves 122. Supply the polymer spinning solution only to the pipe bodies 112b, 112d, 112f, 112g, 112h, 112i, or close the specific supply valve 122, and the nozzle pipe 112a at a specific position among the nozzle pipes arranged in the nozzle block 111. The nozzles in the spinning solution main tank 120 by opening and closing the supply valve 122, for example, to block the supply of the polymer spinning solution only to the 112c and 112e. The supply of the polymer spinning solution to be supplied to the (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is adjusted and controlled.

On the other hand, the polymer spinning solution supplied to each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) through the solution supply pipe 121 in the spinning solution main tank 120 is the solution supply pipe It is supplied to each nozzle 111a provided in the nozzle pipe | tube 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through the nozzle supply pipe 125 extended to 121. As shown in FIG.

That is, each of the nozzles 111a provided in the solution supply pipe 121 and the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i is addressed to the nozzle supply pipe 125, and The nozzle supply pipe 125 is branched to correspond to the number of nozzles 111a.

Here, the nozzle supply pipe 125 is provided with a radiation dose adjusting means (not shown), the radiation dose adjusting means is composed of a nozzle valve (126).

Thus, the nozzle valve 126 is provided as the radiation amount adjusting means to individually control the supply of the polymer spinning solution supplied from the nozzle supply pipe 125 to each nozzle 111a by opening and closing the nozzle valve 126. The nozzle valve 126 is controllably connected to a control unit (not shown), but the opening and closing of the nozzle valve 126 are preferably controlled automatically by the control unit. It is also possible that the opening and closing of the nozzle valve 126 is controlled manually.

In one embodiment of the present invention, but the radiation amount adjusting means is composed of a nozzle valve 126, if it is easy to control and control the radiation amount of the polymer spinning solution to be emitted after being supplied to the nozzle 111a from the nozzle pipe 112 The radiation dose adjusting means may be made of various other structures and means, but is not limited thereto.

By the above structure, the solution supply pipe 121 and the nozzles 111a are connected and installed, and the nozzle valve 126 is provided in the nozzle supply pipe 125 which is branched, respectively, and the spinning solution main tank 120 is provided. When the supply of the polymer spinning solution to each nozzle (111a) through each nozzle pipe (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) in the nozzle nozzle 126 of the plurality of nozzle valve 126 ), The polymer spinning solution is electrospun selectively in the nozzle 111a at a specific position among the nozzles 111a provided in the nozzle bodies 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i. Or a specific nozzle valve 126 to close the nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i of each of the nozzles (111a) provided in the nozzle 111a at a specific position By selectively blocking the electrospinning of the spinning solution, the nozzle pipe 112a in the spinning solution main tank 120 by the nozzle valve 126. The supply of the polymer spinning solution supplied to each nozzle 111a through 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i is individually controlled and controlled.

In an embodiment of the present invention, the supply valve 122 is provided in the solution supply pipe 121 so that each nozzle pipe 112a, 112b, 112c, 112d, 112e of the nozzle block 111 in the spinning solution main tank 120 is provided. , 112f, 112g, 112h, and 112i, and control the supply amount of the polymer spinning solution supplied to the nozzle and the nozzle supply pipe 125 is provided with a nozzle pipe 112a, 112b, 112c, 112d , 112e, 112f, 112g, 112h, 112i and the nozzle pipe 112a, 112b, 112c, 112d, 112e, 112f, by adjusting and controlling the radiation amount of the polymer spinning solution electrospun through each nozzle (111a) The nanofibers having different basis weights are formed in the longitudinal direction of the substrate 115 by the polymer spinning solution electrospun from the nozzles 111a of 112g, 112h, and 112i, but the nozzles are formed on the nozzle block 111. After arranging 111a), each nozzle 111a is directly adjusted and controlled individually. By through the respective nozzles (111a) adjusting and controlling the amount of radiation of the polymer spinning solution to be electrospun and can be made to form a laminate having a basis weight different from the nanofibers in the longitudinal direction of the base material 115, and the like.

The MD direction used in the present invention means Machine Direction, which means the longitudinal direction corresponding to the advancing direction in the case of continuous production of fibers such as film or nonwoven fabric, and the CD direction refers to the perpendicular direction of the CD direction as Cross Direction. . MD may also refer to machine direction / longitudinal direction, and CD to width direction / lateral direction.

On the other hand, the overflow device 200 is provided in the electrospinning apparatus 1 according to the present invention.

That is, each unit (10a, 10b) of the electrospinning device (1) in the spinning solution main tank 8, the second transfer pipe 216, the second transfer control device 218 and the intermediate tank 220 and regeneration Each overflow device 200 including a tank 230 is provided.

In an embodiment of the present invention, each of the units 10a and 10b of the electrospinning apparatus 1 is provided with an overflow device 200, but any one unit 10a of each of the units 10a and 10b is provided. The overflow device 200 is provided, and the unit 10b located at the rear end of the overflow device 200 may be integrally connected.

By the structure as described above, the spinning solution main tank 8 stores the spinning solution serving as a raw material of the nanofibers. In the spinning solution main tank (8) is provided with a stirring device (211) for preventing separation or solidification of the spinning solution.

The second conveying pipe 216 is composed of pipes and valves 212, 213, and 214 connected to the spinning solution main tank 8 or the regeneration tank 230, and the spinning solution main tank 8 or regeneration. The spinning solution is transferred from the tank 230 to the intermediate tank 220.

The second transfer control device 218 controls the transfer operation of the second transfer pipe 216 by controlling the valves 212, 213, 214 of the second transfer pipe 216. The valve 212 controls the transfer of the spinning solution from the spinning solution main tank 8 to the intermediate tank 220, and the valve 213 transfers the spinning solution from the regeneration tank 230 to the intermediate tank 220. To control. The valve 214 controls the amount of polymer spinning solution flowing into the intermediate tank 220 from the spinning solution main tank 8 and the regeneration tank 230.

The control method as described above is controlled according to the liquid level of the spinning solution measured by the second sensor 222 provided in the intermediate tank 230 to be described later.

The intermediate tank 220 stores the spinning solution supplied from the spinning solution main tank 8 or the regeneration tank 230, supplies the spinning solution to the nozzle block 11, and adjusts the liquid level of the supplied spinning solution. The second sensor 222 to measure is provided.

The second sensor 222 may be a sensor capable of measuring the liquid level, and is preferably made of, for example, an optical sensor or an infrared sensor.

The lower portion of the intermediate tank 220 is provided with a supply pipe 240 and a supply control valve 242 for supplying the spinning solution to the nozzle block 11, the supply control valve 242 is the supply pipe 240 Control the supply operation.

The regeneration tank 230 has a stirring device 231 for storing the spinning solution recovered by overflow and preventing separation or solidification of the spinning solution, and measuring a liquid level of the recovered spinning solution. 232 is provided.

The first sensor 232 may be a sensor capable of measuring the liquid level, and for example, it is preferable that the first sensor 232 is formed of an optical sensor or an infrared sensor.

On the other hand, the spinning solution overflowed from the nozzle block 11 is recovered through the spinning solution recovery path 250 provided under the nozzle block 11. The spinning solution recovery path 250 recovers spinning solution to the regeneration tank 230 through the first transfer pipe 251.

The first transfer pipe 251 includes a pipe and a pump connected to the regeneration tank 230, and transfers the spinning solution from the spinning solution recovery path 250 to the regeneration tank 230 by the power of the pump. .

At this time, the regeneration tank 230 is preferably at least one, in the case of two or more may be provided with a plurality of the first sensor 232 and the valve 233.

Subsequently, when there are two or more regeneration tanks 230, a plurality of valves 233 positioned above the regeneration tank 230 are also provided, so that a first transfer control device (not shown) is provided in the regeneration tank 230. Control two or more valves 233 located above the liquid level of the first sensor 232 to control whether the spinning solution is transferred to any one of the plurality of regeneration tanks 230. do.

On the other hand, the electrospinning apparatus 1 is provided with a VOC recycling apparatus 300. That is, a condenser for condensing and liquefying VOCs (Volatile Organic Compounds) generated during spinning of the polymer spinning solution through the nozzles 12 on the units 10a and 10b of the electrospinning apparatus 1. And a distillation apparatus 320 for distilling and liquefying VOC condensed through the condenser 310 and a solvent storage device 330 for storing the liquefied solvent through the distillation apparatus 320. The VOC recycling apparatus 300 is provided.

Here, the condenser 310 is preferably made of a water-cooled, evaporative or air-cooled condenser, but is not limited thereto.

Meanwhile, the vaporized VOC generated in each of the units 10a and 10b is introduced into the condenser 310, and the liquefied VOC generated in the condenser 310 is stored in the solvent storage device 330. Pipings 311 and 331 for connecting are respectively installed.

That is, pipes 311 and 331 for connecting the units 10a and 10b and the condenser 310 and the condenser 310 and the solvent storage device 330 are connected to each other.

In an embodiment of the present invention, the condensed VOC is condensed through the condenser 310, and the condensed liquefied VOC is supplied to the solvent storage device 330, but the condenser 310 and the solvent storage are provided. It is also possible to provide a distillation apparatus 320 between the apparatus 330 to separate and classify each solvent when one or more solvents are applied.

Here, the distillation apparatus 320 is connected to the condenser 310 to heat and vaporize the liquefied state of the VOC with high temperature heat, and is cooled again to supply the liquefied VOC to the solvent storage device (330).

In this case, the VOC recycling apparatus 300 supplies condensation and liquefaction by supplying air and cooling water to the vaporized VOCs discharged through the units 10a and 10b and the condenser 310. Including the distillation apparatus 320 and the solvent storage device 330 for storing the liquefied VOC through the distillation apparatus 320 by applying heat to the condensed VOC to make the vaporized state, and then cooled again to a liquefied state It is composed.

Here, the distillation apparatus 320 is preferably made of a fractional distillation apparatus, but is not limited thereto.

That is, piping for connecting the units 10a and 10b and the condenser 310, the condenser 310 and the distillation apparatus 320, and the distillation apparatus 320 and the solvent storage device 330 to each other ( 311, 321, and 331 are connected to each other.

Subsequently, the content rate of the solvent in the spinning solution overflowed and collected in the regeneration tank 230 is measured. The measurement can be carried out by extracting a portion of the spinning solution in the regeneration tank 230 as a sample, and analyzing the sample. Analysis of the spinning solution can be carried out by a known method.

Based on the measurement result as described above, the required amount of solvent is supplied to the regeneration tank 230 through the pipe 332 of the liquefied VOC supplied to the solvent storage device 330. That is, the liquefied VOC is supplied to the regeneration tank 230 in a required amount according to the measurement result, and can be reused and recycled as a solvent.

Here, the case 18 constituting the units 10a and 10b of the electrospinning apparatus 1 is preferably made of a conductor, but the case 18 is made of an insulator or the case 18 is made of conductive material. The body and the insulator may be mixed and applied, or may be made of various other materials.

In addition, when the upper portion of the case 18 is made of an insulator and the lower portion thereof is mixed with a conductor, the insulating member 19 may be removed. To this end, the case 18 is preferably formed of a single case 18 is coupled to the lower portion formed of a conductor and the upper portion formed of an insulator, but is not limited thereto.

As described above, the case 18 is formed of a conductor and an insulator, and the upper part of the case 18 is formed of an insulator, and is separately provided to attach the collector 13 to the upper inner surface of the case 18. It is possible to delete the insulating member 19, which can simplify the configuration of the device.

In addition, the insulation between the collector 13 and the case 18 can be optimized, and when the electrospinning is performed by applying 35 kV between the nozzle block 11 and the collector 13, the collector 13 and the case 18. It is possible to prevent breakdown of insulation which may occur between (18) and other members.

In addition, the leak current can be stopped within a predetermined range, so that the current supplied from the voltage generators 14a and 14b can be monitored, and an abnormality of the electrospinning apparatus 1 can be detected early, thereby the electrospinning apparatus The long time continuous operation of (1) is possible, nanofiber production of the required performance is stable, and mass production of nanofibers is possible.

Here, the thickness a of the case 18 formed of an insulator is made to satisfy "a = 8mm".

This prevents dielectric breakdown that may occur between the collector 13 and the case 18 and other members when 40 kV is applied between the nozzle block 11 and the collector 13 to perform electrospinning. The leakage current can be limited within a predetermined range.

In addition, the distance between the inner surface of the case 18 formed of an insulator and the outer circumferential surface of the collector 13 is between the thickness a of the case 18 and the inner surface of the case 18 and the outer surface of the collector 13. The distance b is made to satisfy "a + b = 80mm".

This prevents dielectric breakdown that may occur between the collector 13 and the case 18 and other members when 40 kV is applied between the nozzle block 11 and the collector 13 to perform electrospinning. The leakage current can be limited within a predetermined range.

On the other hand, the temperature control device 60 is provided in each tube 40 of the nozzle block 11 installed in each unit 10a, 10b of the electrospinning apparatus 1 according to the present invention, and the voltage generator 14a, 14b).

That is, as shown in Figure 4, the tubular body 40 of the nozzle block 11 is installed in each of the units (10a, 10b), the polymer spinning solution is supplied to a plurality of nozzles 12 provided thereon ) Is provided with a temperature control device (60).

Here, the flow of the polymer spinning solution in the nozzle block 11 is supplied to each tube 40 through a solution flow pipe from the spinning solution main tank 8 in which the polymer spinning solution is stored.

In addition, the polymer spinning solution supplied to each of the tubular bodies 40 is discharged and sprayed through a plurality of nozzles 12 and integrated in the long sheet 15 in the form of nanofibers.

A plurality of nozzles 12 in the longitudinal direction are mounted on the upper portion of each of the tubular body 40 at regular intervals, and the nozzle 12 and the tubular body 40 are made of a conductive member and the tubular body 40 in an electrically connected state. ) Is mounted.

Here, in order to control the temperature control of the polymer spinning solution supplied and introduced into each of the tubular body 40, the temperature control device 60 is a heating wire (41, 42) or pipe 43 provided on the inner periphery of the tubular body (40) )

And, in order to adjust the temperature of the plurality of tubular body 40 is provided with a temperature control device (60).

At this time, as shown in Figures 5 to 6, the thermostat device 60 in the form of a hot wire 41 is formed spirally on the inner circumference of the tubular body 40 of the nozzle block 11 to the tubular body 40 It is preferred to be made to control the temperature of the polymer spinning solution supplied and introduced.

In one embodiment of the present invention is provided in the spiral shape of the temperature control device 60 in the form of a heating wire 41 in the inner circumference of the tubular body 40 of the nozzle block 11, as shown in Figures 7 to 8 In addition, a plurality of temperature regulating devices 60 in the form of hot wires 42 may be provided radially on the inner circumference of the tubular body 40, as shown in FIGS. 9 to 10, in the form of the pipe 43. It is also possible that the temperature control device 60 of the tubular body 40 is provided in a substantially "C" form.

On the other hand, the present invention is to increase the efficiency of electrospinning by using a high concentration of the polymer solution to be reused after the overflow instead of maintaining a constant concentration, but by constantly adjusting the viscosity of the polymer solution using the temperature control device (60) It provides a means and excellent scattering properties at high temperature conditions to control the high viscosity without the use of a diluent can facilitate the formation of nanofibers of the polymer solution.

Viscosity refers to the ratio of the skew stress and skew rate of the solute and solvent in the flowing liquid. It is usually expressed in terms of viscoelasticity per cut area and the unit is dynscm-2gcm-1s-1 or poise (P). The viscosity decreases in inverse proportion to the temperature rise. The viscosity of the solution is higher than that of the solvent because the flow of the liquid is skewed depending on the solute, and the flow rate of the liquid is reduced by that amount.

The viscosity of the solution was measured at various concentrations of the solution, and extrapolated to the concentration 0, the relationship between the intrinsic viscosity (η) and the molecular weight M of the substance can be expressed as (η) = KMa. K and a at this time are integers which depend on a kind of a solute or a solvent, and temperature. Therefore, the viscosity value is affected by temperature and the degree of change depends on the type of fluid. Therefore, when talking about viscosity, you must specify the values of temperature and viscosity.

When manufacturing the nanofibers by the electrospinning apparatus (1), the fiber diameter of the nanofibers, such as the type of polymer and solvent used, the concentration of the polymer solution, the temperature and humidity of the spinning room, It is known to affect radioactivity. That is, the physical properties of the polymer (polymer solution) radiated by electrospinning is important. In general, the viscosity of the polymer during electrospinning has been considered necessary to maintain a certain viscosity or less. This is due to the property that the higher the viscosity, the spinning of the nano-thickness fibers through the nozzle is not made smoothly, the higher the viscosity is not suitable for the fiber through the electrospinning.

The present invention is characterized in that it comprises a temperature control device 60 for maintaining the fiber viscosity suitable for electrospinning as described above.

The temperature control device 60 may include any one or both of a heating device capable of maintaining a low viscosity of a high viscosity polymer solution reused through overflow and a cooling device capable of maintaining a high viscosity of a relatively low viscosity polymer solution. It can be provided.

In the temperature of the electrospinning region, the temperature of the region where electrospinning occurs (hereinafter referred to as the 'spinning region') changes the surface tension of the spinning solution by changing the viscosity of the spinning solution, so that the diameter of the nanofibers spun Will affect.

That is, when the viscosity of the solution is low because the temperature of the radiation region is relatively high, the fiber becomes thinner than the fiber diameter, and when the viscosity of the solution is high because the temperature is relatively low, the fiber diameter is relatively thick.

In particular, in the case of the polymer solution, the concentration of the polymer solution re-supplied through the overflow tends to increase. By measuring the concentration of the polymer solution in the intermediate tank 220, the temperature is controlled using a temperature-viscosity graph according to the corresponding concentration. The viscosity can be kept constant.

The concentration measuring device for measuring the concentration may be a contact type and a non-contact type directly contacting the solution, and the contact type may be a capillary concentration measuring device or a disc (DISC) concentration measuring device. Concentration measuring apparatus or concentration measuring apparatus using infrared light can be used.

The heating device of the present invention may be made of an electric heater, a hot water circulation device or a warm air circulation device, etc., in addition to the devices that can increase the temperature in a range equivalent to the above devices can be borrowed.

As an example of the heating device, the electric heating heater may be used in the form of a hot wire, and the coil wires 62a and 62b may be mounted inside the tubular body 43 of the nozzle block 110, which may be transformed into a jacket ( 5 to 10).

In addition, it is also possible to have a configuration of the hot wires (62a, 62b) of the linear form and the pipe 63 of the U-shape.

Such a heating apparatus includes a nozzle block 110 in which the polymer solution is radiated, a tank (main storage tank, an intermediate tank or a regeneration tank) in which the polymer solution is stored, and an overflow system 200, in particular, transferred from the recovery part to the regeneration tank. It may be provided in any one or more of the transfer piping).

The cooling device of the present invention may be used, such as a cooling means including a chilling device, means for maintaining a constant viscosity of the polymer solution is typically applicable. The cooling device may be provided in any one or more of the nozzle block 110, the tank, and the overflow system 200 in the same manner as the heating device, and is used to maintain a constant viscosity of the polymer solution.

In addition, the temperature control device 60 of the present invention includes a sensor for measuring the concentration and thus a temperature control controller (not shown) for controlling the temperature.

The sensor is installed in the main storage tank 210, the intermediate tank 220, the regeneration tank 230, the nozzle block 110 or the overflow system 200, and the like to measure the concentration of the spinning solution in real time to adjust the temperature Operate the heating and / or cooling device at 60 to keep the viscosity constant.

The concentration of the polymer solution re-supplied through the overflow system 200 of the present invention is 20 to 40%, which is a higher concentration of solution than the concentration of 10 to 18% of the polymer solution used in conventional electrospinning.

In addition, in order to make the viscosity of the polymer solution to be resupply constant of the present invention, the temperature of the polymer solution according to the concentration of the polymer solution is characterized in that it is adjusted to 45 to 120 ℃, not room temperature, more preferably 50 To 100 ° C.

Meanwhile, the polymer solution of the present invention preferably has a viscosity of 1,000 to 5,000 cps, more preferably 1,000 to 3,000 cps. If the viscosity is 1,000 cps or less, the quality of the nanofibers laminated by electrospinning is poor, and if the viscosity is 3,000 cps or more, the discharge of the polymer solution from the nozzle 42 is not easy during electrospinning, and thus the production speed is slowed.

In addition, the present invention, as the electrospinning proceeds, the viscosity of the polymer solution is constant, so that it is excellent in the easiness of spinning during electrospinning and the concentration of the polymer solution is increased, thereby increasing productivity by increasing the amount of solids excluding the solvent in the nanofibers concentrated on the collector. This has the effect of increasing.

In addition, the amount of the remaining solvent of the nanofibers using the electrospinning is less than when using the conventional electrospinning it can be produced a nanofiber of excellent quality.

In addition, the temperature control device 60 of the present invention to control the viscosity of the polymer solution through the temperature control of the nozzle block 110 or the main storage tank 210 by measuring the concentration of the intermediate tank 220 in the offline phase. At the same time, it is possible to control the temperature of the solution according to the concentration measurement through the automatic control system on-line as well as possible.

Here, as illustrated in FIG. 11, the auxiliary feeder for adjusting the feed rate of the long sheet 15 drawn and fed into each unit 10a, 10b of the electrospinning apparatus 1 according to the present invention ( 16).

The auxiliary conveying device 16 is adapted to the conveying speed of the long sheet 15 so as to easily detach and convey the long sheet 15 attached to the collector 13 installed in each unit 10a or 10b by electrostatic attraction. It is configured to include a secondary belt 16a for synchronously rotating and the secondary belt roller 16b for supporting and rotating the secondary belt 16a.

The auxiliary belt 16a is rotated by the rotation of the auxiliary belt roller 16b by the structure as described above, and the long seat 15 is moved to the units 10a, 10b by the rotation of the auxiliary belt 16a. The auxiliary belt roller 16b of one of the auxiliary belt rollers 16b is rotatably connected to the motor for drawing and supplying.

In one embodiment of the present invention, the auxiliary belt 16a is provided with five auxiliary belt rollers 16b, and the auxiliary belt 16a is rotated by rotating one of the auxiliary belt rollers 16b by the operation of the motor. At the same time, the remaining auxiliary belt roller 16b is rotated, but at least two auxiliary belt rollers 16b are provided on the auxiliary belt 16a, and any one of the auxiliary belt rollers 16b is rotated by the operation of the motor. Accordingly, the auxiliary belt 16a and the remaining auxiliary belt roller 16b may be rotated.

On the other hand, in one embodiment of the present invention, but the auxiliary conveying device 16 is composed of an auxiliary belt roller 16b and an auxiliary belt 16a which can be driven by a motor, as shown in Figure 12, the auxiliary belt It is also possible for the roller 16b to consist of a roller with a low coefficient of friction.

At this time, the auxiliary belt roller 16b is preferably made of a roller including a low friction coefficient bearing.

In one embodiment of the present invention, but the auxiliary conveying device 16 is composed of the auxiliary belt 16a and the auxiliary belt roller 16b having a low coefficient of friction, only the roller having a low coefficient of friction excluding the auxiliary belt 16a is provided. It is also possible to be made to convey the long sheet (15).

In addition, in one embodiment of the present invention, a roller having a low friction coefficient is applied as the auxiliary belt roller 16b, but a roller having a low friction coefficient is not limited to its shape and configuration, and may include rolling bearings, oil bearings, ball bearings, Rollers including bearings such as roller bearings, sliding bearings, sleeve bearings, hydraulic journal bearings, hydrostatic journal bearings, pneumatic bearings, pneumatic bearings, pneumatic bearings and air bearings can be applied, and plastics, emulsifiers, etc. It is also possible to apply a roller that reduces the coefficient of friction by including the material and additives.

On the other hand, the thickness measuring device 70 is provided in the electrospinning apparatus 1 according to the present invention.

That is, as shown in Figure 1, the thickness measuring device 70 is provided between each unit (10a, 10b) of the electrospinning apparatus 1, the two measured by the thickness measuring device 70 The feed rate V and the nozzle block 11 are controlled according to the thickness.

When the thickness of the nanofibers discharged from the unit 10a located at the tip end of the electrospinning apparatus 1 is measured to be thinner than the deviation amount, the transfer speed V of the next unit 10b is measured. The thickness can be increased by increasing the discharge amount of the nozzle block 11 or increasing the discharge amount of the nanofibers per unit area by adjusting the voltage intensity of the voltage generators 14a and 14b.

In addition, when the thickness of the nanofibers discharged from the unit 10a located at the tip of the electrospinning apparatus 1 is measured to be thicker than the deviation amount, the feed rate V of the next unit 10b is increased or the nozzle block is made faster. By reducing the discharge amount of (11) and controlling the intensity of the voltage of the voltage generators 14a and 14b, the discharge amount of the nanofibers per unit area can be reduced to reduce the stacking amount, thereby making the thickness thin. A filter having a thickness can be produced.

Here, the thickness measuring device 9 is disposed to face up and down, with the long sheet 15 being introduced and supplied therebetween, and the distance to the top or bottom of the long sheet 15 by an ultrasonic measuring method. It is provided with a thickness measuring section made of a pair of ultrasonic longitudinal wave measuring method.

Thus, the thickness of the long sheet 15 may be calculated based on the distance measured by the pair of ultrasonic measuring devices. That is, by projecting the ultrasonic longitudinal wave and the transverse wave together on the long sheet 15 in which the filters are stacked, the time when each ultrasonic signal of the longitudinal wave and the transverse wave reciprocates in the long sheet 15, that is, the propagation time of the longitudinal wave and the transverse wave, is measured. Thereafter, the measured object using the measured propagation time of the longitudinal wave and the transverse wave, and the propagation speed of the longitudinal wave and the transverse wave, and the temperature constant of the longitudinal wave and the transverse wave propagation speed at the reference temperature of the long sheet 15 on which the filters are stacked. It is a thickness measuring device that uses ultrasonic longitudinal and transverse waves to calculate the thickness of the beam.

In other words, the thickness measuring device 70 measures the propagation time of the longitudinal wave and the transverse wave of the ultrasonic wave, and then measures the propagation time of the measured longitudinal wave and the transverse wave and the longitudinal wave and the transverse wave at the reference temperature of the long sheet 15. By calculating the thickness of the long sheet 15 in which the nanofiber nonwoven fabric is laminated from a predetermined equation using the propagation speed and the temperature constants of the longitudinal wave and the transverse wave propagation speed, the propagation speed according to the temperature change even when the internal temperature is uniform. The thickness can be precisely measured by self-compensating the error caused by the change, and the precise thickness can be measured regardless of any type of temperature distribution inside the filter.

On the other hand, the feed rate and nozzle block 11 of the long sheet 15 by measuring the thickness of the filter of the long sheet 15 to be transported after the polymer spinning solution is injected and laminated to the electrospinning apparatus 1 according to the present invention Although the thickness measuring device 70 is provided to control the elongated sheet feeding speed adjusting device 30 for adjusting the feeding speed of the long sheet 15 in the electrospinning apparatus 1.

Here, the long sheet conveying speed adjusting device 30 is provided on the buffer section 31 and the buffer section 31 formed between each unit (10a, 10b) of the electrospinning device 1 is a long sheet It comprises a pair of support rollers (33, 33 ') for supporting the (15) and an adjusting roller 35 provided between the pair of support rollers (33, 33').

At this time, the support rollers 33 and 33 'are long sheet sheets for transporting the long sheet 15 in which the filters are laminated by the spinning solution sprayed by the nozzles 12 in the units 10a and 10b. It is for supporting the conveyance of 15), and is provided at the line and the rear end of the buffer section 31 formed between the units 10a and 10b, respectively.

And, the adjustment roller 35 is provided between the pair of support rollers (33, 33 '), the elongated sheet (15) is wound, by the up and down movement of the adjustment roller 35 The feed speed and travel time of the long sheets 15a and 15b for each unit 10a and 10b are adjusted.

To this end, a sensing sensor (not shown) is provided for detecting a feed speed of the long sheets 15a and 15b in each of the units 10a and 10b, and in each unit 10a and 10b detected by the sensing sensor. The main control unit 7 for controlling the movement of the adjustment roller 35 in accordance with the feed speed of the long sheet (15a, 15b) is provided.

In one embodiment of the present invention, the sensing speed of the long sheet (15a, 15b) in each of the units (10a, 10b), and the controller according to the feed rate of the detected long sheet (15a, 15b) control roller ( 35 is configured to control the movement, but the auxiliary belt 16a or the auxiliary belt for driving the auxiliary belt 16a provided on the outside of the collector 13 to transfer the long sheet (15a, 15b). The driving speed of the roller 16b or the motor (not shown) may be sensed, and accordingly, the controller may be configured to control the movement of the adjustment roller 35.

According to the structure as described above, the long sheet in the unit 10b in which the feed rate of the long sheet 15a in the unit 10a in which the sensing sensor is positioned at the front end of each unit 10a or 10b is located in the rear end thereof. When detecting that the feed rate is higher than 15b), as shown in FIGS. 13 to 14, the pair of long sheets 15a to be transported in the unit 10a positioned at the distal end may be prevented from sagging. A unit 10b disposed between the supporting rollers 33 and 33 'and positioned at the rear end of the unit 10a positioned at the front end while moving the adjusting roller 35 on which the long sheet 15 is wound downward. The tip of the long sheet 15a, which is conveyed to the outside of the unit 10a positioned at the front end and is excessively transferred to the buffer section 31 positioned between the units 10a and 10b, is pulled out by Of the long sheet 15a in the unit 10a located at The long sheet 15a is prevented from sagging and wrinkled while being corrected and controlled so that the feeding speed of the long sheet 15b in the unit 10b positioned at the same is the same.

On the other hand, the feed rate of the long sheet 15b in the unit 10b in which the sensing speed of the built-in chuck sheet 15a of the unit 10a positioned at the front end of each of the units 10a and 10b is located at the rear end thereof. If it is detected that the slower, as shown in Figs. 15 to 16, the pair of support rollers 33 to prevent the long sheet 15b to be transported in the unit 10b located at the rear end thereof is torn. , 33 '), which is conveyed to the unit 10b positioned at the rear end of the unit 10a positioned at the front end while moving the adjusting roller 35 on which the long sheet 15 is wound upward. The long sheet 15a, which is transported to the outside of the unit 10a positioned at the tip of the sheet 15 and is wound by the adjusting roller 35, in the buffer section 31 positioned between each unit 10a, 10b. When long in the unit 10a located at the front end by supplying it quickly to the unit 10b located at the rear end (15a), the feed rate of the feed rate and the unit (10b) within the elongated sheet (15b) which is located in its rear end and to a correction control such that the same prevents the dead of the elongated sheet (15b).

The unit located at the rear end of each unit 10a by adjusting the conveying speed of the long sheet 15b conveyed into the unit 10b at the rear end of each unit 10a, 10b by the structure as mentioned above. It is possible to obtain the effect that the feed rate of the long sheet 15b in 10b is equal to the feed rate of the long sheet 15a in the unit 10a positioned at its tip.

On the other hand, the air permeability measuring device 80 is provided in the electrospinning apparatus 1 according to the present invention.

That is, the air permeability measuring device for measuring the air permeability of the filter manufactured through the electrospinning device 1 in the rear of the unit (10d) located at the rear end of each unit (10a, 10b) of the electrospinning device (1) 80 is provided.

As described above, the air permeability of the long sheet 15 and the nozzle block 11 are controlled based on the air permeability of the filter measured by the measuring device 80.

When the air permeability of the nanofiber nonwoven fabric discharged through the units 10a and 10b of the electrospinning apparatus 1 is largely measured as described above, the feed rate V of the unit 10b located at the rear end is slowed, or By increasing the discharge amount of the nozzle block 11, and controlling the intensity of the voltage of the voltage generating device (14a, 14b) to increase the discharge amount of the nanofiber per unit area to form a small ventilation.

When the air permeability of the nanomembrane discharged through the units 10a and 10b of the electrospinning apparatus 1 is measured small, the feed rate V of the unit 10b located at the rear end is increased or the nozzle is increased. By reducing the discharge amount of the block 11, and controlling the intensity of the voltage of the voltage generators (14a, 14b) to reduce the discharge amount of the nanofiber per unit area to reduce the amount of lamination to form a large air permeability.

As described above, by measuring the air permeability of the filter, it is possible to manufacture a filter having a uniform air permeability by controlling the feed speed and the nozzle block 11 of each unit 10a, 10b according to the air permeability.

Here, if the air permeability of the filter is less than the predetermined value, the feed rate V is not changed from the initial value, and if the deviation P is greater than or equal to the predetermined value, the feed rate V is initialized. Since it is also possible to control to change from a value, it becomes possible to simplify control of the feed rate V by the feed rate V control apparatus.

In addition, the discharge amount and the intensity of the voltage of the nozzle block 11 can be adjusted in addition to the control of the feed rate V. When the air permeability deviation amount P is less than the predetermined value, the discharge amount and the intensity of the voltage of the nozzle block 11 are controlled. Is not changed from the initial value, and when the deviation amount P is equal to or greater than a predetermined value, the discharge amount and voltage of the nozzle block 11 are controlled to change the intensity of the discharge amount and voltage of the nozzle block 11 from the initial value. The control of the intensity of the simplification can be simplified.

Here, the electrospinning apparatus (1) is provided with a main control device (7), the main control device (7) is a nozzle block 11, voltage generators (14a, 14b) and thickness measuring device (70) and The long sheet feed rate adjusting device 30 and the ventilation device also controls the measuring device 80.

In the present invention, the elongated sheet 15 uses a substrate selected from cellulose, a bicomponent system, and polyterephthalate.

Cellulose base material used in the present invention is preferably composed of 100% cellulose composition ratio, cellulose and polyethylene terephthalate (PET) relative to the total mass of cellulose consisting of 70 ~ 90: 10 ~ 30 mass% ratio It is also possible to use a base material, and to use the thing by which the cellulose base material was flame-resistant coated.

The bicomponent substrate may be selected from a sheath-core, a side by side, and a C-type.

On the other hand, the laminating device 90 for laminating the electromembrane nanomembrane through each unit (10a, 10b) of the electrospinning apparatus 1 is located in the rear end of the unit (10a, 10b) ) Is provided at the rear, and performs the post-process of the filter electrospun through the electrospinning apparatus (1) by the laminating device (90).

On the other hand, the present invention may include an adhesive layer on the nanofiber layer.

Hereinafter, an electrospinning apparatus for manufacturing a filter including an adhesive layer will be described with reference to FIGS. 17 to 21.

FIG. 17 is a side view schematically showing an electrospinning apparatus for manufacturing a filter including an adhesive layer, and FIG. 18 schematically shows a nozzle block installed in an adhesive (low melting point polymer) unit of an electrospinning apparatus according to the present invention. 19 is a plan view schematically showing a nozzle block installed in an adhesive (low melting point polymer) unit of the electrospinning apparatus according to the present invention, and FIGS. 20 to 21 are shown in each unit of the electrospinning apparatus according to the present invention. A plan view schematically illustrating an operation process of sequentially spraying an adhesive (low melting point polymer) and a polymer spinning solution through a nozzle block to be installed.

As shown in the figure, the electrospinning apparatus 1 according to the present invention is composed of a bottom-up electrospinning apparatus, at least one unit (10a, 10b, 10c, 10d, 10e) is provided at a predetermined interval spaced sequentially Through each unit (10a, 10b, 10c, 10d, 10e), the polymer spinning solution of the same material or other materials of the same material in the upper direction individually or electrospinning the polymer spinning solution of different materials to the electrospinning filter Manufacture.

In one embodiment of the present invention, the electrospinning apparatus 1 is composed of a bottom-up electrospinning apparatus, but may be made of a top-down electrospinning apparatus (not shown).

In addition, in one embodiment of the present invention, five units (10a, 10b, 10c, 10d, 10e) of the electrospinning apparatus 1 is provided, but the unit (10a, 10b, 10c, 10d, 10e) of the The number is preferably provided with two or more, but is not limited thereto.

Here, each unit (10a, 10b, 10c, 10d, 10e) of the electrospinning apparatus 1 is a solution main tank (8) and the respective solutions in which an adhesive (low melting point polymer) or a polymer spinning solution is filled therein. Metering pump (not shown) for quantitatively supplying the adhesive (low melting point polymer) or polymer spinning solution filled in the main tank 8 and the adhesive (low melting point polymer) or polymer filled in each of the solution main tanks 8 Spray the spinning solution, the nozzle block 11 in which a plurality of nozzles (12) in the form of pins are arranged and the nozzle (11) to accumulate the adhesive (low melting point polymer) or polymer spinning solution sprayed from the nozzle 12 ( 12) and a collector 13 spaced at a predetermined interval, and a voltage generator (14a, 14b, 14c, 14d, 14e) for generating a voltage to the collector (13).

In the electrospinning apparatus 1 according to the present invention by the above structure, the adhesive (low melting point polymer) or polymer spinning solution filled in each solution main tank 8 is continuously connected to the nozzle block 11 through a metering pump. The adhesive (low melting polymer) or the polymer spinning solution supplied to the nozzle block 11 is injected and focused on the collector 13 under high voltage through a plurality of nozzles 12. Nanofibers and adhesives (low melting point polymers) are laminated on the collector 13 to produce a filter.

To this end, each unit (10a, 10b, 10c, 10d, 10e) of the electrospinning device 1 is made of a spinning solution unit (10a, 10c, 10e) and adhesive (low melting point polymer) (10b, 10d), The polymer spinning solution is injected from the nozzle block 11a in the spinning solution units 10a, 10c, and 10e located at the front end, and the nozzle block 11b in the adhesive (low melting polymer) units 10b and 10d located at the rear end thereof. ), The spinning solution unit 10a, 10c, 10e and the adhesive (low melting point polymer) units 10b, 10d are alternately provided in the electrospinning apparatus 1, respectively, such that the adhesive (low melting point polymer) is electrospun. The spinning solution and the adhesive (low melting point polymer) are alternately sprayed on (13).

In addition, the nozzle block 11a in the middle use liquid unit 10a, 10c, 10e of the nozzle block 11 installed in each of the units 10a, 10b, 10c, 10d, and 10e includes a solution main tank filled with a spinning solution ( 8, the nozzle block 11b in the adhesive (low melting polymer) units 10b, 10d is connected to a solution main tank 8 filled with the adhesive (low melting polymer).

In an embodiment of the present invention, each nozzle block 11 installed in each of the units 10a, 10b, 10c, 10d, and 10e is individually connected to the corresponding number of solution main tanks 8 to form an adhesive (low Melting point polymer) or a polymer spinning solution is supplied, but the spinning solution units 10b, 10d, and 10e of the units 10a, 10b, 10c, 10d, and 10e are supplied to one solution main tank 8. It is also possible to be configured to be connected to supply the polymer spinning solution, the adhesive (low melting point polymer) units (10a, 10c) is also connected to one solution main tank (8) to receive the adhesive (low melting point polymer).

Here, the nozzle 12 in a partial form in a specific region of the nozzle block (11a) installed in the adhesive (low melting point polymer) unit (10b, 10d, 10e) of each of the units (10a, 10b, 10c, 10d, 10e). The nozzle 12, which is installed in this arrangement and installed in a partial form in a specific area of the nozzle block 11a, is connected to a solution main tank 8 filled with an adhesive (low melting point polymer) to form an adhesive (low melting point polymer). The supplied adhesive (low melting point polymer) is sprayed onto the first nanofiber layer.

In the nozzle 12 arranged in a partial form in the specific region of the nozzle block 11a by the structure as described above, the adhesive in the form and region of the specific region and the specific portion of the first nanofibrous layer and the second nanofiber layer (Low melting point polymer) is injected.

In one embodiment of the present invention, although the nozzles 12 are partially arranged in a specific area of the nozzle block 11a, the adhesive (low melting polymer) units 10b and 10d are anisotropically used liquid units 10a and 10c. In the same way as 10e, the nozzle block 11a is provided with a nozzle tube 40 in which a plurality of nozzles 12 are arranged in the longitudinal direction, and each nozzle tube 40 is

It is made to be opened and closed individually by a supply pipe (not shown) and a valve (not shown), and each nozzle 12 is branched into a plurality of supply pipes (not shown), each of the supply pipes are individually by a valve (not shown) It is made to be opened and closed respectively, and the specific region and the specific portion of the first nanofibrous layer and the second nanofiber layer by spraying an adhesive (low melting point polymer) only in the nozzle 12 provided in a partial form in a specific region by adjusting the respective valves. It is also possible to spray the adhesive (low melting point polymer) in the form of regions and parts.

At this time, each nozzle pipe (40) arranged in the nozzle block (11a) is connected to the solution main tank (8) filled with an adhesive (low melting point polymer) through a supply pipe and a valve, respectively, each nozzle pipe ( A plurality of nozzles 12 provided in the 40 is connected to the nozzle pipe 40, each of which is addressed to each of the plurality of supply pipes branched and controlled by each valve to control the adhesive (low melting point polymer) in the form of a specific nozzle only area and part ) Is sprayed.

When the adhesive (low melting point polymer) unit (10b, 10d) is made of the same structure as the spinning solution unit (10a, 10c, 10e), the nozzle tube (40) and the nozzle tube (40) of the nozzle block (11a) Nozzle (12) provided in each of the) is individually controlled to control and control the injection position of the adhesive (low melting point polymer) on the first nanofiber layer, the shape and shape of the spraying area of the adhesive (low melting point polymer), etc. At the same time, various adjustments and controls such as spraying sequence of adhesive (low melting point polymer) and polymer spinning solution are possible.

As described above, during the electrospinning of the polymer spinning solution on the first nanofibrous layer and the second nanofiber layer, an adhesive (low melting point polymer) is first sprayed onto a specific region and part on the first nanofibrous layer and the second nanofibrous layer. Thereby preventing the detachment phenomenon occurring in the second nanofibrous layer which is electrospun onto the first nanofiber layer and the first nanofibrous layer, and the third nanofibrous layer which is electrospun onto the second nanofiber layer and formed to be laminated. By spraying the adhesive (low melting point polymer) only to specific regions and portions of the 1 nanofibrous layer and the second nanofiber layer, the injected adhesive (low melting point polymer) minimizes interference of the polymer spinning solution electrospun, thereby It can improve performance and quality.

In one embodiment of the present invention, although a plurality of nozzles 12 are arranged in a partial form at specific edges of each of the nozzle blocks 11a, the nozzles 12 are arranged in the nozzle block 11a. The area, shape, and position of) are not limited thereto.

Here, the valve is provided in each of the supply pipe of the plurality of nozzles 12 arranged in a partial form in a particular region of the nozzle block (11a), the nozzle 12 is provided in a partial form in a specific region by the valve It is also possible for the nozzle to be individually controlled to spray the adhesive (low melting point polymer) to the substrate 15 in a specific region and partial form while forming another shape and shape.

Here, the front of the unit (10a) located at the top of each unit (10a, 10b, 10c, 10d, 10e) of the electrospinning apparatus 1 is supplied into the unit (10a) and the adhesive (low melting point polymer) and A feed roller 3 is provided for supplying the substrate 15 on which nanofibers are alternately sprayed by the electrospinning of the polymer spinning solution, and located at the rear end of each unit 10a, 10b, 10c, 10d, 10e. At the rear of the unit 10e, a winding roller 5 for winding the substrate 15 on which the adhesive (low melting point polymer) and the nanofibers are laminated is provided.

In addition, in each unit 10a, 10b, 10c, 10d, 10e of the electrospinning apparatus 1, the substrate 15 introduced and fed through the feed roller 3 is transferred to the take-up roller 5 side. It is configured to further include an auxiliary feeder 16 for adjusting the feed rate of the substrate 15 at the same time.

And, the electrospinning apparatus 1 is provided with a main control device 7, the main control device is a nozzle block 11 installed in each unit (10a, 10b, 10c, 10d, 10e), auxiliary transport device 16 and the voltage generators 14a, 14b, 14c, 14d, 14e, and at the same time are connected to the thickness measuring device 70, the substrate feed rate adjusting device 30 and the air permeability measuring device 80, which will be described later To control this.

Meanwhile, a laminating apparatus 90 for laminating nanofibers electrospun on the substrate 15 through each unit 10a, 10b, 10c, 10d, 10e of the electrospinning apparatus 1 includes the respective units ( It is provided at the rear of the unit (10e) located at the end of the 10a, 10b, 10c, 10d, 10e, the post-process of the filter electrospun through the electrospinning device (1) by the laminating device (90) Perform.

As described above, the substrate 15 through which the polymer spinning solution is electrospun and the nanofibers are laminated while passing through the units 10a, 10b, 10c, 10d, and 10e of the electrospinning apparatus 1 is a release paper film. It is preferable to spin the polymer spinning solution on the collector 13 without the substrate 15.

At this time, the polymer spinning solution radiated through each unit 10a, 10b, 10c, 10d, 10e of the electrospinning apparatus 1 is the same as described above. In addition, the polymer used as the adhesive is not particularly limited, but is preferably at least one selected from the group consisting of low melting point polyurethanes, low melting point polyesters and low melting point polyvinylidene fluorides.

At this time, the low melting point polyvinylidene fluoride (PVDF) used in the present invention has a melting point of 80 to 160 ℃.

There are various ways to control the melting point of PVDF, and generally, a method of controlling the synthesis of PVDF copolymer and a method of controlling the PVDF weight average molecular weight.

As one of the methods for producing low melting point PVDF, it is preferable to adjust the content of the comonomer to control the synthesis of the copolymer. In the present invention, as the polyvinylidene fluoride (PVDF) polymer, it is preferable to use a polyvinylidene fluoride (PVDF) copolymer having a comonomer content of 5 to 50% by weight. The comonomer is tetrafluoroethylene (TFE), trifluoroethylene, hexafluoroisobutylene, perfluorobutyl ethylene, perfluoro, in addition to hexafluoropropylene (HFP) or chlorotrifluoroethylene (CTFE). Low profile vinyl ether (PPVE), perfluoro ethyl vinyl ether (PEVE), perfluoro methyl vinyl ether (PMVE), perfluoro-2,2-dimethyl-1,3-dioxol (PDD) and perfluor Rho-2-methylene-4-methyl-1,3-dioxolane (PMD) and the like may be used, and among these, hexafluoropropylene (HFP) or chlorotrifluoroethylene (CTFE) may be preferably used. However, it is not limited to this kind.

In addition, the melting point of the polymer can be controlled by adjusting the weight average molecular weight due to the characteristics of the polymer. In the present invention, the weight average molecular weight of the polyvinylidene fluoride (PVDF) polymer having a melting point of 80 to 160 ° C is 3,000 to 30,000. It is desirable to adjust. If the weight average molecular weight exceeds 30,000, the melting point exceeds 160 ℃, if less than 3,000 melting point is less than 80 ℃ bar efficiency of electrospinning is inferior.

In addition, it is preferable to use terephthalic acid, isophthalic acid and mixtures thereof as the low melting polyester. In order to further lower the melting point, ethylene glycol may be added as a diol component.

The low melting point polyurethane uses a mixture of a polymerization degree polyurethane having a softening temperature of 80-100 ° C. and a high polymerization degree polyurethane having a softening temperature of 140 ° C. or higher.

The low melting point polyvinylidene fluoride, the low melting point polyester, and the low melting point polyurethane can be used alone or in combination of two or more.

In addition, the polymer spinning solution supplied through the nozzle 12 in the units 10a and 10c positioned at the front end of each of the units 10a, 10b, 10c, 10d, and 10e may be a polymer having a synthetic resin material capable of electrospinning. As a solution dissolved in a suitable solvent, the kind of solvent is not limited as long as it can dissolve the polymer, and is the same as described above.

Here, the overflow device 200 is provided in the electrospinning apparatus 1. That is, each of the units 10a, 10b, 10c, 10d, and 10e of the electrospinning apparatus 1 is intermediate with each of the solution main tank 8, the second transfer pipe 216, and the second transfer control device 218. The overflow device 200 which consists of the structure containing the tank 220 and the regeneration tank 230 is provided, respectively.

In one embodiment of the present invention, each of the units 10a, 10b, 10c, 10d, 10e of the electrospinning apparatus 1 is provided with an overflow device 200, but each of the units (10a, 10b, 10c) , 10d, 10e, any one unit (10a) is provided with an overflow device 200, the remaining unit (10b, 10c, 10d, 10e) is formed in a structure that is integrally connected to the overflow device 200 It is also possible, and the overflow device 200 is applied to the adhesive (low melting point polymer) units 10b, 10d, and 10e that spray the adhesive (low melting point polymer) among the units 10a, 10b, 10c, 10d, and 10e. The overflow apparatus 200 may be provided respectively in the spinning solution units 10a and 10c respectively provided or electrospinning the polymer spinning solution.

In addition, the overflow device 200 is provided in any one unit 10b to which an adhesive (low melting point polymer) is injected among the units 10a, 10b, 10c, 10d, and 10e of the electrospinning apparatus 1, One of the units 10d and 10e is integrally connected to the overflow device 200, or a polymer spinning solution is electrospun among the units 10a, 10b, 10c, 10d, and 10e to form nanofibers. The overflow device 200 may be provided in one unit 10a that is stacked, and the other unit 10c may be integrally connected to the overflow device 200.

According to the structure as described above, the solution main tank 8 provided in the heavy adhesive (low melting polymer) unit 10b, 10d, 10e of each unit (10a, 10b, 10c, 10d, 10e) is an adhesive ( The low melting point polymer) stores, and the solution main tank 8 provided in the spinning solution units 10a and 10c stores the polymer spinning solution serving as a raw material of the nanofibers. In the solution main tank 8, a separate stirring device 211 for preventing separation and coagulation of the adhesive (low melting point polymer) and the polymer spinning solution is provided therein.

The second transfer pipe 216 includes a pipe (not shown) and valves 212, 213, and 214 connected to the solution main tank 8 or the regeneration tank 230. (Low melting point polymer) or a solution in which the polymer spinning solution is filled is transferred from the main tank 8 or the regeneration tank 230 to the intermediate tank 220 with an adhesive (low melting point polymer) or polymer spinning solution.

On the other hand, the second transfer control device 218 controls the transfer operation of the second transfer pipe 216 by controlling the valve (212, 213, 214) of the second transfer pipe 216.

Here, the valve 212 controls the transfer of the adhesive (low melting point polymer) or polymer spinning solution from the solution main tank (8) filled with adhesive (low melting point polymer) or polymer spinning solution, The valve 213 controls the transfer of adhesive (low melting point polymer) or polymer spinning solution from the regeneration tank 230 to the intermediate tank 220, and the valve 214 is a solution main tank 8 and the regeneration tank ( The amount of the adhesive (low melting point polymer) or the polymer spinning solution introduced into the intermediate tank 220 is controlled at 230.

As described above, the liquid level of the adhesive (low melting point polymer) or the polymer spinning solution measured through the second sensor 222 provided in the intermediate tank 230 described later by the control of the valves 212, 213, and 214. The height is controlled.

The intermediate tank 220 stores the adhesive (low melting polymer) or the polymer spinning solution supplied from the solution main tank 8 or the regeneration tank 230 filled with the adhesive (low melting polymer) or the polymer spinning solution separately. Among the nozzle blocks 11, the adhesive (low melting point) is formed by the nozzle block 11a provided in the adhesive (low melting point polymer) units 10a and 10c and the nozzle block 11b provided in the spinning solution units 10a and 10c. The second sensor 222 for supplying the polymer and the polymer spinning solution, and for measuring the liquid level of the supplied adhesive (low melting point polymer) and the polymer spinning solution is provided.

Here, the second sensor 222 is preferably made of a sensor capable of measuring the liquid level of the adhesive (low melting point polymer) or the polymer spinning solution such as an optical sensor or an infrared sensor, but is not limited thereto.

Meanwhile, a supply pipe 240 and a supply control valve 242 for supplying an adhesive (low melting point polymer) or a polymer spinning solution to the nozzle block 11 are respectively provided below the intermediate tank 220. The control valve 242 controls the supply operation of the adhesive (low melting point polymer) or the polymer spinning solution through the supply pipe 240.

The regeneration tank 230 separately stores the adhesive (low melting point polymer) or polymer spinning solution recovered by overflow, and agitating device for preventing separation and solidification of the adhesive (low melting point polymer) or polymer spinning solution ( 231 is provided therein.

Here, the first sensor 232 is preferably made of a sensor capable of measuring the liquid level of the adhesive (low melting point polymer) or the polymer spinning solution such as an optical sensor or an infrared sensor, but is not limited thereto.

Meanwhile, the adhesive (low melting point polymer) or the polymer spinning solution overflowed from the nozzle block 11 is separately recovered through the solution recovery path 250 provided at the lower part of the nozzle block 11, and the solution recovery is performed. The path 250 recovers the polymer spinning solution in the regeneration tank 230 through the first transfer pipe 251.

In addition, the first transfer pipe 251 is configured to include a pipe (not shown) and a pump (not shown) connected to the regeneration tank 230, the adhesive (low melting point polymer) and the power of the pump and The polymer spinning solution is transferred from the solution recovery path 250 to the regeneration tank 230.

In this case, it is preferable that the regeneration tank 230 is provided with at least one. When the regeneration tank 230 is provided with two or more, the first sensor 232 and the valve 233 are provided in plural numbers. It is desirable to be.

Here, when the regeneration tank 230 is provided with two, the number of valves 233 located above the regeneration tank 230 is also provided in the corresponding number, thereby the first transfer control device (not shown) The adhesive (low-melting polymer) or by controlling the two or more valves 233 located on the upper side in accordance with the liquid level of the first sensor 232 provided in the regeneration tank 230 or

Controls whether the polymer spinning solution is individually transferred to the regeneration tank 230 among the plurality of regeneration tanks 230.

On the other hand, the electrospinning apparatus 1 is an auxiliary transport device 16, a moving speed adjusting device 30, a temperature control device 60, a thickness measuring device 70, air permeability measuring device 80, VOC recycling device ( 300, etc., wherein the auxiliary feeder, moving speed adjusting device, temperature adjusting device, thickness measuring device, air permeability measuring device, and VOC recycling device are the same as described above. In addition, the case 18 which comprises each unit of the said electrospinning apparatus 1 is also the same as that mentioned above.

Hereinafter, a method of manufacturing a filter including the first spinning solution nanofiber and the second spinning solution nanofiber of the present invention using the electrospinning device will be described.

First, the first spinning solution is supplied to the spinning solution main tank 8 connected to the first unit 10a of the electrospinning apparatus, and the second spinning solution is connected to the second unit 10b of the electrospinning apparatus. A plurality of nozzle block 11 of the nozzle block 11 is supplied to the tank (8), and the first and second spinning liquid supplied to the spinning solution main tank (8) is provided with a high voltage through a metering pump (not shown). The nozzle 12 is continuously metered in. The first and second spinning solutions supplied from the nozzles 12 are electrospun and focused on the collector 13 subjected to the high voltage through the nozzles 12, and the first nanofibrous layer and the second spinning solution are concentrated. The nanofiber layer is laminated. Here, the nanofibers stacked in the units 10a and 10b of the electrospinning apparatus 1 are rotated by the supply roller 3 and the supply roller 3 which are operated by driving of a motor (not shown). The first nanofibrous layer and the second nanofiber layer on the collector 13 are transferred from the first unit 10a to the second unit 10b by the rotation of the auxiliary feeder 16 to be driven, and the above process is repeated. This is successively electrospun and laminated.

In the process of electrospinning the first spinning solution on the collector 13 to form a stack, the first nanofibrous layer is formed in the first unit 10a by varying the spinning conditions for each unit 10a, 10b of the electrospinning apparatus. The stack is formed, and the second nanofibrous layer is continuously stacked in the second unit 10b.

The voltage generator 14a, which is installed in the first unit 10a of the electrospinning apparatus 1 and supplies voltage to the first unit 10a, provides a low radiation voltage and collects the first nanofiber layer as the collector 13. And a voltage generator 14b installed in the second unit 10b to supply a voltage to the second unit 10b to give a high radiation voltage so that the second nanofiber layer is formed on the first nanofiber layer. Laminated to At this time, the radiation voltage applied by each of the voltage generators 14a and 14b is 1 kV or more, preferably 15 kV or more, and the voltage applied by the voltage generator 14a of the first unit 10a is the second unit 10b. It is characterized in that the lower than the voltage applied by the voltage generator 14b, but is not limited thereto.

In the present invention, the voltage of the first unit 10a of the electrospinning apparatus 1 is lowered to stack the first nanofiber layer on the collector, and the voltage of the second unit 10b is applied to the second nanofiber layer. The filter is manufactured by stacking the particles. However, it is also possible that the first nanofiber layer is spun and stacked in the first unit 10a and the second nanofiber layer is spun in the second unit 10b by varying the intensity of the voltage.

In addition, the number of units of the electrospinning apparatus 1 is composed of three or more, and the voltage is different for each unit so that at least three first nanofiber layers or second nanofiber layers having different fiber diameters are arranged on the collector 13. It will also be possible to produce laminated filters.

By the same method as described above, the first polymer solution is electrospun on the collector 13 in the first unit 10a to form a first nanofiber layer, and in the second unit 10b, a second nanofiber layer is formed on the first nanofiber layer. After the polymer solution is electrospun and the second nanofibrous layer is laminated, it is possible to manufacture the filter of the present invention through a process of heat fusion.

Here, the first polymer solution used in accordance with a suitable embodiment of the present invention is characterized in that the one selected from the group consisting of polyethersulfone, polyacrylonitrile, polyvinyl alcohol, polyamide and hydrophilic polyurethane, The second polymer solution is one selected from the group consisting of polyvinylidene fluoride, low melting polyester and hydrophobic polyurethane.

In addition, the first polymer solution used according to another suitable embodiment of the present invention is a heat resistant polymer, the second polymer solution is polyacrylonitrile, polyvinyl alcohol, polyamide, hydrophilic polyurethane, polyvinylidene fluoride , Low melting point polyester and hydrophobic polyurethane is characterized in that one selected from the group consisting of.

Hereinafter, the present invention will be described in detail by way of Examples, but the following Examples and Experimental Examples are only illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. .

Example 1

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and charged into the main tank of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus, The low melting polymer solution supplied to the main tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from each of the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m ^{2 while} being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. Form.

Next, the polymer spinning solution in which polyacrylonitrile was dissolved in a DMF solvent was supplied to the main tank 8 connected to the spinning solution unit 10b of the electrospinning apparatus, and the polymer spinning solution in which hydrophobic polyurethane was dissolved in DMAc solvent was released. The main tank 8 is connected to the working liquid unit 10d. The polyacrylonitrile solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump (not shown). A nanofiber layer is formed.

Then, the low melting polymer solution is discharged from the low melting polymer unit 10c through a nozzle to form another adhesive layer on the first nanofiber layer, and is supplied to the main tank 8 connected to the spinning solution unit 10d. The hydrophobic polyurethane solution is electrospun through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer.

On the other hand, the substrate is a spinning solution in the low melting polymer unit by the rotation of the feed roller 3 and the auxiliary feeder 16 driven by the rotation of the feed roller 3 is driven by the drive of a motor (not shown) The mask pack is manufactured by electrospinning the first and second nanofiber layers on the substrate while being transferred to the unit and repeating the above process.

Comparative Example 1 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 1 without forming an adhesive layer.

Desorption test of nano fiber layer

The occurrence of nanofiber delamination was visually observed and the results are shown in Table 1.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 1 NO NO NO NO NO NO NO Comparative Example 1 NO Desorption after 3 days

Skin adhesion test

 It was applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional mask pack samples without nanofibers were evaluated as controls and the results are shown in Table 2.

Sample Skin adhesion Example 1 Good Comparative Example 1 Good Control Bad

Skin soothing and moisturizing test

A mask pack was prepared in the same manner as in Example 1, using hydrophilic polyvinylidene fluoride, polyacrylonitrile (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as a polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 3 by weight%.

Raw material name Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

 After using it three times, the degree of soothing and moisturizing the skin is measured on a 5-point scale. 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point: Very bad After the evaluation, each average value is shown in Table 4 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 1 4.5 Comparative Example 2 3.3 Comparative Example 3 3.2 Comparative Example 4 2.5 Comparative Example 5 2.7

Example 2

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and charged into the main tank of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus, The low melting polymer solution supplied to the main tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from each of the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m ^{2 while} being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. Form.

Next, a polymer spinning solution in which polyvinyl alcohol is dissolved in a DMF solvent is supplied to a main tank 8 connected to the spinning solution unit 10b of the electrospinning apparatus, and a polymer spinning solution in which a hydrophobic polyurethane is dissolved in a DMAc solvent is used as a spinning solution. The main tank 8 is connected to the unit 10d. The polyvinyl alcohol solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump (not shown), and thus the first polyvinyl alcohol solution is first sprayed on the adhesive layer. The nanofiber layer is formed.

Then, the low melting polymer solution is discharged from the low melting polymer unit 10c through a nozzle to form another adhesive layer on the first nanofiber layer, and is supplied to the main tank 8 connected to the spinning solution unit 10d. The hydrophobic polyurethane solution is electrospun through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer.

On the other hand, the substrate is a spinning solution in the low melting polymer unit by the rotation of the feed roller 3 and the auxiliary feeder 16 driven by the rotation of the feed roller 3 is driven by the drive of a motor (not shown) The mask pack is manufactured by electrospinning the first and second nanofiber layers on the substrate while being transferred to the unit and repeating the above process.

Comparative Example 6 Preparation of Mask Pack without Adhesive Layer

The mask pack was prepared in the same manner as in Example 1 without forming an adhesive layer.

Desorption test of nano fiber layer

 The occurrence of nanofiber delamination was visually observed and the results are shown in Table 5.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 1 NO NO NO NO NO NO NO Comparative Example 1 NO Desorption after 3 days

In the mask pack of the present invention, even after 15 days, no delamination of the nanofibers occurred, but in the mask pack without the adhesive layer, nanofiber delamination occurred after 3 days.

Skin adhesion test

 It was applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated using as controls and the results are shown in Table 6.

Sample Skin adhesion Example 1 Good Comparative Example 1 Good Control Bad

Evaluation Example 3 Skin Calm & Moisturizing Effect Test

A mask pack was prepared in the same manner as in Example 2, using hydrophilic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as a polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 7 by weight%.

Raw material name Example 2 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the degree of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each average value is shown in Table 8 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 2 4.5 Comparative Example 7 3.3 Comparative Example 8 3.2 Comparative Example 9 2.5 Comparative Example 10 2.7

Example 3

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and was put in the main tanks of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus. Subsequently, polyacrylonitrile and polyvinyl alcohol having a weight average molecular weight (Mw) of 157,000 were dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution, which was then used as a spinning solution unit (10b, 10d) into the main tank. In the low melting point polymer unit, the electrode and the collector were electrospun at a distance of 40 cm, an applied voltage of 20 kV, and 70 ° C. to form an adhesive layer having a basis weight of 0.1 g / m ² on the polyethylene terephthalate substrate, and then to the electrode in the spinning solution unit 10b. The distance between the collectors was electrospun at 40 cm, an applied voltage of 15 kV, and 70 ° C. to form a first nanofiber layer having a basis weight of 0.5 g / m ² . Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning was again performed by electrospinning the distance between the electrode and the collector in the spinning solution unit (10d) at 40cm, applied voltage 25kV, 70 ℃ to prepare a mask pack by laminating a second nanofiber layer having a basis weight of 0.5g / m ² .

Comparative Example 11 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 1 without forming an adhesive layer.

Desorption test of nano fiber layer

 The occurrence of nanofiber delamination was visually observed and the results are shown in Table 9.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 3 NO NO NO NO NO NO NO Comparative Example 11 NO Desorption after 3 days

Skin adhesion test

 It was applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional mask pack samples without nanofibers were evaluated as controls and the results are shown in Table 10.

Sample Skin adhesion Example 3 Good Comparative Example 11 Good Control Bad

From the results in Table 2, it can be seen that the mask pack including the nanofiber layer as in the present invention exhibits better skin adhesion than the conventional nonwoven mask pack.

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 3, using hydrophilic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 11 by weight%.

Raw material name Example 3 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

 After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: very good, 4 points: slightly good, 3 points: normal, 2 points: slightly bad, 1 point : After evaluating on a very poor scale, each mean value is shown in Table 12 as a result of skin soothing and moisturizing effects when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 3 4.5 Comparative Example 12 3.3 Comparative Example 13 3.2 Comparative Example 14 2.5 Comparative Example 15 2.7

Example 4

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and was put in the main tanks of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus. Subsequently, polyacrylonitrile and polyvinyl alcohol having a weight average molecular weight (Mw) of 157,000 were dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution, which was then used as a spinning solution unit (10b, 10d) into the main tank. In the low melting polymer unit, the distance between the electrode and the collector was 40 cm, an applied voltage of 20 kV, and 70 ° C., which was then electrospun to form an adhesive layer having a basis weight of 0.1 g / m ² on the cellulose substrate, and then between the electrode and the collector in the spinning solution unit 10b. The first nanofibrous layer having a basis weight of 0.5 g / m ² was formed by laminating a distance at 40 cm, an applied voltage of 15 kV, and 70 ° C. Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning was again performed by electrospinning the distance between the electrode and the collector in the spinning solution unit (10d) at 40cm, applied voltage 25kV, 70 ℃ to prepare a mask pack by laminating a second nanofiber layer having a basis weight of 0.5g / m ² .

Comparative Example 16 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 4 without forming an adhesive layer.

Desorption test of nano fiber layer

 The occurrence of nanofiber delamination was visually observed and the results are shown in Table 13.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 4 NO NO NO NO NO NO NO Comparative Example 16 NO Desorption after 3 days

Skin adhesion test

Mask pack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional mask pack samples without nanofibers were evaluated as controls and the results are shown in Table 14.

Sample Skin adhesion Example 4 Good Comparative Example 16 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 4, using hydrophilic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 15 by weight%.

Raw material name Example 4 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

 After 10 times of use 3 times, the degree of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each average value is shown in Table 16 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 4 4.5 Comparative Example 17 3.3 Comparative Example 18 3.2 Comparative Example 19 2.5 Comparative Example 20 2.7

Example 5

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and was put in the main tanks of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus. Subsequently, a polyacrylonitrile having a weight average molecular weight (Mw) of 157,000 and a polyvinylidene fluoride having a weight average molecular weight of 50,000 were dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution. These were put into the main tanks of the spinning solution units 10b and 10d, respectively. In the low melting point polymer unit, the electrode and the collector were electrospun at a distance of 40 cm, an applied voltage of 20 kV, and 70 ° C. to form an adhesive layer having a basis weight of 0.1 g / m ² on the polyethylene terephthalate substrate, and then to the electrode in the spinning solution unit 10b. The distance between the collectors was electrospun at 40 cm, an applied voltage of 15 kV, and 70 ° C. to form a first nanofiber layer (polyacrylonitrile) having a basis weight of 0.5 g / m ² . Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning and again to form a second nanofiber layer (polyvinylidene fluoride) having a basis weight of 0.5g / m ² by electrospinning the distance between the electrode and the collector in the spinning solution unit 10d at 40cm, applied voltage 25kV, 70 ℃ To prepare a mask pack.

Comparative Example 21 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 5 without forming an adhesive layer.

Desorption test of nano fiber layer

For the mask pack sample, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 17.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 5 NO NO NO NO NO NO NO Comparative Example 21 NO Desorption after 3 days

Skin adhesion test

Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated as controls and the results are shown in Table 18.

Sample Skin adhesion Example 5 Good Comparative Example 21 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 5 using hydrophilic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 19 by weight%.

Raw material name Example 5 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the degree of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each average value is shown in Table 20 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 5 4.5 Comparative Example 22 3.3 Comparative Example 23 3.2 Comparative Example 24 2.5 Comparative Example 25 2.7

Example 6

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and was put in the main tanks of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus. Subsequently, a polyacrylonitrile having a weight average molecular weight (Mw) of 157,000 and a polyvinylidene fluoride having a weight average molecular weight of 50,000 were dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution. This was put into the main tank of each spinning solution unit 10b, 10d. In the low melting point polymer unit, the distance between the electrode and the collector was 40 cm, the applied voltage was 20 kV, and 70 ° C., which was then electrospun to form an adhesive layer having a basis weight of 0.1 g / m 2 on the cellulose substrate, and then the distance between the electrode and the collector in the spinning solution unit 10b. 0.5g / m2 by electrospinning at 40cm, applied voltage 15kV, 70 ℃ A phosphorous first nanofiber layer (polyacrylonitrile) was formed by lamination. Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning again and the electrospinning distance between the electrode and the collector at 40cm, applied voltage 25kV, 70 ℃ in the spinning solution unit (10d) to laminate a second nanofiber layer (polyvinylidene fluoride) of 0.5g / ㎡ basis weight A mask pack was prepared.

Comparative Example 26 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 6 without forming an adhesive layer.

Desorption test of nano fiber layer

For mask pack samples, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 21.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 6 NO NO NO NO NO NO NO Comparative Example 26 NO Desorption after 3 days

Skin adhesion test

 Mask pack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional mask pack samples without nanofibers were evaluated as controls and the results are shown in Table 22.

Sample Skin adhesion Example 6 Good Comparative Example 26 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 6 using hydrophilic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 23 by weight%.

Raw material name Example 6 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each mean value is shown in Table 24 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 6 4.5 Comparative Example 27 3.3 Comparative Example 28 3.2 Comparative Example 29 2.5 Comparative Example 30 2.7

Example 7

The low-polymerization polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to 25% by weight to prepare a low-melting polymer solution, and was put in the main tanks of the low-melting polymer unit (10a, 10c) of the electrospinning apparatus. Subsequently, polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 was dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution, which was then prepared in the spinning solution unit (10b, 10d). It was put in the main tank. In the low melting point polymer unit, the electrode and the collector were electrospun at 40 cm, an applied voltage of 20 kV, and 70 ° C. to form an adhesive layer having a basis weight of 0.1 g / m 2 on the polyethylene terephthalate substrate, followed by the electrode and collector in the spinning solution unit 10b. Distance of 40cm, applied voltage 15kV, electrospinning at 70 ℃, basis weight 0.5g / ㎡ The first nanofiber layer was formed by laminating. Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning was again performed by electrospinning the distance between the electrode and the collector in the spinning solution unit (10d) at 40cm, applied voltage 25kV, 70 ℃ to prepare a mask pack by laminating a second nanofiber layer having a basis weight of 0.5g / ㎡.

Comparative Example 31 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 7, without forming an adhesive layer.

Desorption test of nano fiber layer

For the maskpack sample, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 25.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 7 NO NO NO NO NO NO NO Comparative Example 31 NO Desorption after 3 days

In the mask pack of the present invention, even after 15 days, no delamination of the nanofibers occurred, but in the mask pack without the adhesive layer, nanofiber delamination occurred after 3 days.

Skin adhesion test

 Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated using the control and the results are shown in Table 26.

Sample Skin adhesion Example 7 Good Comparative Example 31 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 7, using hydrophobic polyvinylidene fluoride, polyvinyl alcohol (PAN), hydrophobic polyurethane (PU), and polyvinyl alcohol (PVA) as a polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 27 by weight%.

Raw material name Example 7 Comparative Example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 PVDF Hydrophobic PVDF PAN Hydrophobic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each average value is shown in Table 28 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 7 4.5 Comparative Example 32 3.3 Comparative Example 33 3.2 Comparative Example 34 2.5 Comparative Example 35 2.7

Example 8

The low melting point polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to prepare a low melting point polymer solution, which was supplied to the main tank 8 connected to the low melting point polymer units 10a and 10c of the electrospinning apparatus. The low melting polymer solution supplied to the tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m 2 while being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. do.

Subsequently, polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 was dissolved in the same solvent of dimethylacetamide (N, N-Dimethylacetamide, DMAc) to prepare a spinning solution, which was then prepared in the spinning solution unit (10b, 10d). It was put in the main tank. In the low melting point polymer unit, the distance between the electrode and the collector was 40 cm, the applied voltage was 20 kV, and 70 ° C., which was then electrospun to form an adhesive layer having a basis weight of 0.1 g / m 2 on the cellulose substrate, and then the distance between the electrode and the collector in the spinning solution unit 10b. 0.5g / m2 by electrospinning at 40cm, applied voltage 15kV, 70 ℃ The first nanofiber layer was formed by laminating. Then, the substrate including the substrate and the first nanofibrous layer laminated thereon is rotated so that the upper and lower sides are inverted by 180 °, and then transferred to the low melting polymer unit 10c to transfer the electricity under the same conditions as 10a. Spinning was again performed by electrospinning the distance between the electrode and the collector in the spinning solution unit (10d) at 40cm, applied voltage 25kV, 70 ℃ to prepare a mask pack by laminating a second nanofiber layer having a basis weight of 0.5g / ㎡.

Comparative Example 36 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 8 without forming an adhesive layer.

Desorption test of nano fiber layer

For the maskpack sample, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 29.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 8 NO NO NO NO NO NO NO Comparative Example 36 NO Desorption after 3 days

Skin adhesion test

Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated using the control and the results are shown in Table 30.

Sample Skin adhesion Example 8 Good Comparative Example 36 Good Control Bad

Skin soothing and moisturizing test

A mask pack was prepared in the same manner as in Example 8, using polyvinyl alcohol (PAN) and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 31 by weight%.

Raw material name Example 8 Comparative Example 37 Comparative Example 38 PVDF PAN PVA Baby 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 Butylene Glycol 8 8 8 Carob bean gum 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 Spices 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluation on a very poor scale, each mean value is shown in Table 32 as a result of skin soothing and moisturizing effects when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 8 4.5 Comparative Example 37 3.3 Comparative Example 38 3.2

Example 9

The low melting point polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to prepare a low melting point polymer solution, which was supplied to the main tank 8 connected to the low melting point polymer units 10a and 10c of the electrospinning apparatus. The low melting polymer solution supplied to the tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m 2 while being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. do.

Next, a polymer spinning solution in which polyurethane was dissolved in a DMF solvent was supplied to a main tank 8 connected to the spinning solution unit 10b of the electrospinning apparatus, and a polymer in which polyvinylidene fluoride having a weight average molecular weight of 50,000 was dissolved in a solvent. The spinning solution is supplied to the main tank 8 connected to the spinning solution unit 10d. The polyurethane solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump (not shown), and the first nanomaterial is deposited on the adhesive layer. A fibrous layer is formed.

Then, the low melting polymer solution is discharged from the low melting polymer unit 10c through a nozzle to form another adhesive layer on the first nanofiber layer, and is supplied to the main tank 8 connected to the spinning solution unit 10d. The polyvinylidene fluoride solution is electrospun through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer.

On the other hand, the substrate is a spinning solution in the low melting polymer unit by the rotation of the feed roller 3 and the auxiliary feeder 16 driven by the rotation of the feed roller 3 is driven by the drive of a motor (not shown) The mask pack is manufactured by electrospinning the first and second nanofiber layers on the substrate while being transferred to the unit and repeating the above process.

Comparative Example 39 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 9 without forming an adhesive layer.

Desorption test of nano fiber layer

For mask pack samples, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 32.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 9 NO NO NO NO NO NO NO Comparative Example 39 NO Desorption after 3 days

Skin adhesion test

Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated using the control and the results are shown in Table 33.

Sample Skin adhesion Example 9 Good Comparative Example 39 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 9 using hydrophilic polyvinylidene fluoride, polyurethane (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 34 by weight%.

Raw material name Example 9 Comparative Example 40 Comparative Example 41 Comparative Example 42 Comparative Example 43 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each mean value is shown in Table 35 as a result of skin soothing and moisturizing effects when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 9 4.5 Comparative Example 40 3.3 Comparative Example 41 3.2 Comparative Example 42 2.5 Comparative Example 43 2.7

Example 10

The low melting point polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to prepare a low melting point polymer solution, which was supplied to the main tank 8 connected to the low melting point polymer units 10a and 10c of the electrospinning apparatus. The low melting polymer solution supplied to the tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m 2 while being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. do.

Next, a polymer spinning solution in which polyvinylidene fluoride having a weight average molecular weight of 50,000 is dissolved in a DMF solvent is supplied to the main tank 8 connected to the spinning solution units 10b and 10d of the electrospinning apparatus. The polyurethane solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump (not shown), and the first nanomaterial is deposited on the adhesive layer. A fibrous layer is formed.

Then, the low melting polymer solution is discharged from the low melting polymer unit 10c through a nozzle to form another adhesive layer on the first nanofiber layer, and is supplied to the main tank 8 connected to the spinning solution unit 10d. The polyvinylidene fluoride solution is electrospun through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer. The applied voltages during the electrospinning of the spinning solution units 10b and 10d were 25 kV and 15 kV, respectively. The substrate is then released from the low melting polymer unit by the rotation of the feed roller 3 operated by the driving of a motor (not shown) and the auxiliary feeder 16 driven by the rotation of the feed roller 3. The mask pack was manufactured by electrospinning the first and second nanofiber layers on the substrate while transferring the used liquid unit to repeating the above process.

Comparative Example 44 Preparation of Mask Pack without Adhesive Layer

A mask pack was prepared in the same manner as in Example 10 without forming an adhesive layer.

Desorption test of nano fiber layer

 For the mask pack sample, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 36.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 10 NO NO NO NO NO NO NO Comparative Example 44 NO Desorption after 3 days

Skin adhesion test

Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated as controls and the results are shown in Table 37.

Sample Skin adhesion Example 10 Good Comparative Example 44 Good Control Bad

Skin soothing and moisturizing test

A mask pack was prepared in the same manner as in Example 10, using hydrophilic polyvinylidene fluoride, polyurethane (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 38 by weight%.

Raw material name Example 10 Comparative Example 45 Comparative Example 46 Comparative Example 47 Comparative Example 48 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each mean value is shown in Table 39 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 10 4.5 Comparative Example 45 3.3 Comparative Example 46 3.2 Comparative Example 47 2.5 Comparative Example 48 2.7

Example 11

The low melting point polyurethane was dissolved in DMAc (N, N-dimethylaceticamide) solvent to prepare a low melting point polymer solution, which was supplied to the main tank 8 connected to the low melting point polymer units 10a and 10c of the electrospinning apparatus. The low melting polymer solution supplied to the tank 8 is continuously metered into the plurality of nozzles 12 of the nozzle block 11 to which a high voltage is applied through a metering pump (not shown). The low melting polymer solution supplied from the nozzles 12 forms an adhesive layer having a basis weight of about 0.1 g / m 2 while being electrospun and focused on a substrate positioned on the collector 13 under high voltage through the nozzles 12. do.

Next, the polymer spinning solution in which the polyurethane is dissolved in the DMAc solvent is supplied to the main tank 8 connected to the spinning solution units 10b and 10d of the electrospinning apparatus. The polyurethane solution supplied to the main tank 8 connected to the spinning solution unit 10b is electrospun through a nozzle block 11 to which a high voltage is applied through a metering pump (not shown), and the first nanomaterial is deposited on the adhesive layer. A fibrous layer is formed.

Then, the low melting polymer solution is discharged from the low melting polymer unit 10c through a nozzle to form another adhesive layer on the first nanofiber layer, and is supplied to the main tank 8 connected to the spinning solution unit 10d. The polyvinylidene fluoride solution is electrospun through the nozzle block 11 to form a second nanofiber layer on the another adhesive layer. The applied voltages during the electrospinning of the spinning solution units 10b and 10d were 28 kV and 18 kV, respectively. The substrate is then released from the low melting polymer unit by the rotation of the feed roller 3 operated by the driving of a motor (not shown) and the auxiliary feeder 16 driven by the rotation of the feed roller 3. The mask pack was manufactured by electrospinning the first and second nanofiber layers on the substrate while transferring the used liquid unit to repeating the above process.

Comparative Example 49 Preparation of a Mask Pack without an Adhesive Layer

A mask pack was prepared in the same manner as in Example 11 without forming an adhesive layer.

Desorption test of nano fiber layer

For the maskpack sample, the occurrence of nanofiber delamination was visually observed and the results are shown in Table 40.

Sample Skin adhesion 1 day 3 days 5 days 7 days 9th 11th 15th Example 11 NO NO NO NO NO NO NO Comparative Example 49 NO Desorption after 3 days

Skin adhesion test

Maskpack samples were applied on the skin surface of five subjects for 30 minutes and the degree of skin adhesion (peel resistance) was evaluated. Conventional maskpack samples without nanofibers were evaluated as controls and the results are shown in Table 41.

Sample Skin adhesion Example 11 Good Comparative Example 49 Good Control Bad

Skin soothing and moisturizing test

The mask pack was prepared in the same manner as in Example 11 but using hydrophilic polyvinylidene fluoride, polyurethane (PAN), hydrophilic polyurethane (PU), and polyvinyl alcohol (PVA) as the polymer spinning solution.

The prepared mask pack was impregnated with the skin active ingredient shown in Table 42 by weight%.

Raw material name Example 11 Comparative Example 50 Comparative Example 51 Comparative Example 52 Comparative Example 53 PVDF Hydrophilic PVDF PAN Hydrophilic PU PVA Baby 1.8 1.8 1.8 1.8 1.8 Tataric Acid 0.12 0.12 0.12 0.12 0.12 Butylene Glycol 8 8 8 8 8 Carob bean gum 2.2 2.2 2.2 2.2 2.2 antiseptic 0.35 0.35 0.35 0.35 0.35 Spices 0.1 0.1 0.1 0.1 0.1 Chamomile Extract 0.5 0.5 0.5 0.5 0.5 Ivy Extract 0.5 0.5 0.5 0.5 0.5 Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount

After 10 times of use 3 times, the level of soothing and moisturizing the skin is 5 points: Very good, 4 points: Slightly good, 3 points: Normal, 2 points: Slightly bad, 1 point : After evaluating on a very poor scale, each mean value is shown in Table 43 as a result of skin soothing and moisturizing effect when using the product.

Skin soothing and moisturizing effect when applying mask pack Example 11 4.5 Comparative Example 50 3.3 Comparative Example 51 3.2 Comparative Example 52 2.5 Comparative Example 53 2.7

As shown in the above results, in the mask pack of the present invention, even after 15 days no delamination of the nanofibers, the mask pack without the adhesive layer occurred nanofiber delamination after 3 days.

In addition, the mask pack including the nanofiber layer as shown in the present invention showed better skin adhesion than the conventional nonwoven mask pack, it was found that the adhesion to the skin, skin soothing and moisturizing effect is remarkably excellent.

While the invention has been shown and described in connection with particular embodiments, it will be appreciated that various modifications and changes can be made without departing from the spirit and scope of the invention as set forth in the appended claims. Anyone who owns it can easily find out.

Claims (17)

A base material; A first nanofiber layer formed by electrospinning a polyacrylonitrile solution; A second nanofiber layer laminated on the first nanofiber layer by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and hydrophobic polyurethane; Mask pack, characterized in that it comprises. A base material; A first nanofiber layer formed by electrospinning a polyvinyl alcohol solution; A second nanofiber layer laminated on the first nanofiber layer by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and hydrophobic polyurethane; Mask pack, characterized in that it comprises. Polyethylene terephthalate substrates; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the polyethylene terephthalate substrate; Mask pack, characterized in that it comprises. A cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the cellulose base; Mask pack, characterized in that it comprises. Polyethylene terephthalate substrates; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane attached to the other side of the polyethylene terephthalate substrate; Mask pack, characterized in that it comprises. A cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophilic polymer solution selected from any one of polyacrylonitrile, polyvinyl alcohol, polyamide, and hydrophilic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane attached to the other side of the cellulose base; Mask pack, characterized in that it comprises. Polyethylene terephthalate substrates; A first nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane formed on one side of the polyethylene terephthalate substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the polyethylene terephthalate substrate; Mask pack, characterized in that it comprises. A cellulose substrate; A first nanofiber layer formed by electrospinning a hydrophobic polymer solution selected from any one of polyvinylidene fluoride and a hydrophobic polyurethane formed on one side of the cellulose substrate; A second nanofiber layer formed by electrospinning the same polymer solution as the first nanofiber layer attached to the other side of the cellulose base; Mask pack, characterized in that it comprises. A base material; A first nanofiber layer formed by electrospinning a polyurethane solution; A second nanofiber layer formed by laminating a polyvinylidene fluoride solution on the first nanofiber layer; Mask pack, characterized in that it comprises. A base material; A first nanofiber layer having a diameter of 80 to 150 nm formed by electrospinning polyvinylidene fluoride; A second nanofiber layer having a diameter of 150 to 300 nm formed by electrospinning polyvinylidene fluoride; Mask pack, characterized in that it comprises. A base material; A first nanofiber layer having a diameter of 80 to 150 nm formed by electrospinning polyurethane; A second nanofiber layer having a diameter of 150 to 300 nm formed by electrospinning polyurethane; Mask pack, characterized in that included. The method according to any one of claims 1 to 11, Bonding between the substrate and the nanofiber layer is a mask pack, characterized in that the adhesive is formed through an adhesive layer formed by electrospinning a low melting polymer solution. The method of claim 12, The low melting polymer solution is a mask pack, characterized in that at least one selected from the group consisting of low melting point polyester, low melting point polyurethane, low melting point polyvinylidene fluoride. The method of claim 12, The low melting polymer solution is a mask pack, characterized in that the electrospinning on the front surface or a portion of the nanofiber layer. The method according to any one of claims 1 to 11, The nanofiber layer is a mask pack, characterized in that formed by electrospinning at a temperature of 50 to 100 ℃. The method of claim 15, The nanofibrous layer is a mask pack, characterized in that the basis weight different in the longitudinal or transverse direction. The method of claim 15, The polymer solution for forming the nanofiber layer is a mask pack, characterized in that the viscosity is maintained at 1,000 cps to 3,000 cps through a temperature control device.

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