KR101811649B1 - Mask and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a method of manufacturing a mask using bottom-up electrospinning, comprising the steps of: preparing a mask including nanofibers having different weights of nanofibers in the MD direction, which are made of a bottom- More particularly, the present invention relates to a method of manufacturing a mask including nanofibers having different weights of nanofibers in the MD direction, characterized in that the basis weight of the nanofibers is operated by an on-off system of a plurality of nozzle tubes. And to nanomembranes produced thereby.

Description

MASK AND METHOD OF MANUFACTURING THE SAME

The present invention relates to a method of manufacturing a mask including nanofibers different in basis weight in a plane direction, and more particularly, to a method of manufacturing a mask including nanofibers differing in basis weight in the MD direction (Machine Direction) Mask.

Facial mask is a thing that shields nose and mouth to prevent inhalation and scattering of germs and dusts of sanitary hygiene. Facial masks have been used since the 1919 Spanish cold, when influenza was prevalent. Currently, facial masks are made of cotton, non-woven fabric, paper and the like.

Conventional facial masks prevent the cold air from being directly blown through the nasal cavity or oral cavity, so that it can prevent some of them from being caught in a cold. However, the size of the pores is much larger than that of microbes or bacteria having a size of 0.1 탆 to 1.0 탆 There is a limitation in blocking microbes such as bacteria and fine dusts.

On the other hand, a nanofiber refers to a microfiber having a diameter of only a few tens to a few hundred nanometers, and is produced by an electric field. That is, nanofibers generate electrical repulsive force inside the polymer material by applying a high voltage electric field to the polymer material, which is the raw material, and the nanofibers are manufactured and produced by breaking the molecules into a nano-sized yarn shape.

At this time, as the electric field becomes stronger, the polymer material as the raw material is finely torn, so that a nanofiber having a thinning of 10 to 1000 nm can be obtained.

In the conventional technology for spinning nanofibers, since it is limited to a small-scale working line focused on a laboratory, there is a demand for a technique of spinning nanofibers by dividing a spinning zone and using a unit concept.

On the other hand, in the conventional electrospinning apparatus, a spinning solution is electrospun on one surface of a substrate supplied from the outside, and a nanomembrane is laminated to produce nanofibers. That is, the conventional electrospinning device comprises a bottom-up or top-down electrospinning device, and the spinning solution is electrospun on only the bottom surface or the top surface of the substrate supplied into the electrospinning device to form a nanomembrane by laminating the nanomembrane.

As described above, since the electrospinning device comprises the bottom-up electrospinning device or the top-down electrospinning device, the spinning solution is electrospun to the bottom surface or the top surface of the substrate supplied from the outside and transported in a predetermined direction, .

As shown in FIG. 1, the top-down electrospinning device of the bottom-up or top-down electrospinning device includes a spinning solution main tank 120 filled with a polymer spinning solution and a polymer spinning solution filled in the spinning solution main tank 120 A nozzle block 111 for discharging the polymer solution in the spinning liquid main tank and having a plurality of nozzles 111a arranged in a pin shape and a nozzle block 111a And a voltage generator 114 for generating a high voltage in the collector 113. The collector 113 is disposed at a predetermined distance from the nozzle 111a in order to accumulate the polymer spinning solution injected from the collector 113, (110, 110 ').

In the method of manufacturing a nanomembrane through the electrospinning device 100, the polymer spinning solution filled in the spinning liquid main tank 120 is continuously and quantitatively supplied to the nozzle block 111 to which a high voltage is applied through the metering pump, The polymer spinning solution supplied to the nozzle block 111 is radiated and focused on the collector 113 to which a high voltage is applied on the base material 115 conveyed in the electrospinning device 100 through the nozzle 111a A nanomembrane is laminated.

At this time, in the electrospinning apparatus 100, the substrate 115 is conveyed by the conveyance belt 116a rotated between the conveyance rollers 116b.

When the nanomembrane prepared by electrospinning the polymer spinning solution through the electrospinning device as described above is applied to a filter material used in an industrial field, the basis weight of the entire nanomembrane used as the filter material must be constant and uniform, It is possible to produce and sell the products satisfactorily. According to the filter used in the gas turbine of the thermal power plant, depending on the direction of the air flow, the position of the air inflow portion, the direction of the air exhaust portion and the position of the exhaust portion, It is necessary that the basis weight of the nanomembrane constituting the filter membrane is not necessarily constant. On the other hand, in the filter section where air filtration is active, the basis weight of the nanomembrane must be controlled to improve the air filtering efficiency, Since the air flow rate is not so large, the basis weight of the nanomembrane is greatly adjusted There is a need for a design that is more durable than the air filtration side.

Thus, the basis weight of the nanomembrane is required to be a nanomembrane material having different basis weights on the same nanomembrane depending on the positions of the air inlet and outlet.

Korean Patent No. 10-1162033 Korean Patent No. 10-1382571

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides a mask including nanofibers different in basis weight in the MD direction among plane directions of the nanofiber layer in order to improve abrasion resistance and productivity at the time of manufacturing a mask, and a method for manufacturing the same .

The present invention provides a method of manufacturing a mask using a bottom-up electrospinning method, wherein a basis weight of the nanofibers in the MD direction, which is made of a bottom-up electrospinning device including a plurality of nozzle tubes in a bottom- .

Further, the basis weight of the nanofibers is characterized by providing a method of manufacturing a mask having different weights of nanofibers in the MD direction, wherein a plurality of nozzle tubes are operated by an on-off system.

In addition, the on-off system is characterized in that the basis weight is alternately designed in the MD direction in which nanofibers are integrated.

In addition, the present invention provides a mask produced by the above manufacturing method.

The present invention can improve durability and productivity of nanofibers by providing a mask including nanofibers having different basis weights in the MD direction, and the nanofiber layer having fine pores can capture microorganisms such as bacteria and fine dusts A mask having an excellent blocking ability against a fine foreign substance and a method of manufacturing the same are provided.

1 is a side view schematically showing a mask electrospinning device,
2 is a plan view schematically showing a nozzle body arranged in a nozzle block of a mask electrospinning apparatus according to the present invention,
3 is a perspective view schematically showing a nozzle body arranged in a nozzle block of a mask electrospinning apparatus according to the present invention,
4 is a side view schematically showing a nozzle body arranged in a nozzle block of a mask electrospinning device according to the present invention,
FIGS. 5 to 6 are diagrams showing an operation process (in FIG. 5, a nozzle closed by a dashed line in FIG. 5) of the polymer spinning solution through the nozzle of each nozzle tube of the mask electrospinning apparatus according to the present invention And the nozzle indicated by the broken line in Fig. 6 is located at the lower part of the substrate)
Figs. 7 to 8 are plan views of masks having different weights in the MD direction produced by the present invention. Fig.

In order to increase the lifetime and efficiency of the mask, different types of nanofibers are used. In addition, the present invention can control the basis weight and fiber diameter of the nanofibers according to the position and direction of the air, A method of manufacturing a mask including nanofibers different in basis weight in the MD direction among planar directions of the nanofibers, and a mask manufactured by the manufacturing method have been considered in order to prevent the loss of life of the fiber, increase the efficiency of the nanofiber, and increase the economical efficiency.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical gist of the present invention.

FIG. 2 is a plan view schematically showing a nozzle body arranged in a nozzle block of a mask electrospinning apparatus according to the present invention. FIG. 3 schematically shows a nozzle body arranged in a nozzle block of a mask electrospinning apparatus according to the present invention. 4 is a side view schematically showing a nozzle body arranged in a nozzle block of the mask electrospinning apparatus according to the present invention, and Figs. 5 to 6 are views showing a nozzle of each nozzle body of the mask electrospinning apparatus according to the present invention, FIG. 2 is a plan view schematically showing an operation process in which a polymer spinning solution is electrospun on the same plane of a substrate. FIG.

Referring to FIG. 1, an electrospinning apparatus 100 according to the present invention includes a bottom-up electrospinning apparatus and at least one unit 110 or 110 '. In one embodiment of the present invention, the electrospinning device 100 is a bottom-up electrospinning device, but it may also be a top-down electrospinning device.

Here, the units 110 and 110 'include a spinning liquid main tank 120 filled with a polymer spinning solution and a metering pump (not shown) for supplying a polymer spinning solution filled in the spinning solution main tank 120 in a fixed amount And a plurality of nozzle tubes 112 having a plurality of nozzles 111a in the form of a pin are arranged in the longitudinal direction of the substrate 115 so as to discharge the polymer solution in the spinning solution main tank 120 A collector 113 disposed at a predetermined distance from the nozzle 111a to accumulate the polymer spinning solution injected from the nozzle block 111 and the nozzle 111a and a voltage generator 113 for generating a high voltage to the collector 113, (114).

As described above, the mask electrospinning device 1 is continuously supplied with a predetermined amount of the polymer spinning solution filled in the spinning liquid main tank 120 into the nozzle block 111 to which a high voltage is applied through the metering pump, The polymer spinning solution supplied to the collector 111 is radiated and focused on the collector 113 on which a high voltage is applied through the nozzle 111a and on the base material 115 conveyed in the electrospinning device so that the nanofibers are laminated .

At this time, the at least one unit 110, 110 'included in the mask electrospinning device 1 is sequentially disposed at a predetermined interval, and the polymer spinning solution is electrospun through each unit 110, 110' A mask is prepared.

The nozzle block 111 of the electrospinning device 100 includes a plurality of nozzle tubes 112 arranged in the longitudinal direction thereof and a spinning liquid main tank for supplying a polymer spinning solution to the nozzle tubes 112 120 are connected to each other.

The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, which are linearly formed on the upper surface of the nozzle block 111 and have a plurality of nozzles 111a linearly, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are arranged in the longitudinal direction of the substrate 115 in the longitudinal direction of the substrate 115, And the polymer spinning solution filled in the spinning solution main tank 120 is supplied.

Here, the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i are connected to the spinning solution main tank 120 through a solution supply tube 121, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and a spinning liquid main tank 120 are branched.

At this time, a supply amount adjusting means (not shown) is connected to the solution supply pipe 121, which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120, And the supply amount adjusting means is composed of a supply valve 122.

A supply valve 122 is provided in the solution supply pipe 121 which is communicated to each nozzle body 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 by the supply valves 122, And controlled on-off systems.

That is, when the polymer spinning solution is supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i from the spinning solution main tank 120 through the solution supply tube 121, By the opening and closing of the supply valve 122 provided in the solution supply pipe 121 for supplying the main tank 120 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle tubes 112b, 112d, 112f, 112g, 112h, 112i at specific positions among the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the nozzle block 111 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i, 112f, 112g, 112h, 112i, 112f, 112h, 112h, 112h, The supply of the polymer solution is controlled and controlled.

For this purpose, the supply valve 122 is preferably controllably connected to a control unit (not shown). Preferably, the opening and closing of the supply valve 122 is automatically controlled by the control unit. However, It is also possible that the opening and closing of the supply valve 122 is manually controlled.

112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120. However, The supply amount adjusting means may be composed of various other structures and means, but the present invention is not limited thereto.

The solution supply pipe 121 is connected to the spinning solution main tank 120 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i, A supply valve 122 is provided at each of the nozzles 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 120 to supply a plurality of 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i arranged in the nozzle block 111 by opening the specific supply valve 122 of the supply valve 122, The nozzle tubular body 112a (112a, 112b, 112d, 112f, 112g, 112h, 112i) at the specific position among the nozzle tubular bodies provided in the nozzle block 111 by supplying the polymer solution, , 112c, and 112e of the spinning liquid main tank 120 are blocked by the opening and closing of the supply valve 122, 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.

The polymer spinning solution supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through the solution supply tube 121 in the spinning solution main tank 120 flows through the solution supply tube 121, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i through a nozzle supply pipe 125 which is connected to the nozzles 121a.

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

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

The supply of the polymer solution to be supplied to each nozzle 111a from the nozzle supply pipe 125 is controlled individually by the nozzle valve 126 by the opening and closing of the nozzle valve 126, Preferably, the nozzle valve 126 is controllably connected to a control unit (not shown), and the opening and closing of the nozzle valve 126 is automatically controlled by the control unit. However, It is also possible that the opening and closing of the nozzle valve 126 are manually controlled.

In the embodiment of the present invention, if the amount of the spinning solution of the polymer spinning solution is easily controlled and controlled after being supplied to the nozzle 111a from the nozzle tube 112, The means for controlling the amount of radiation may be composed of various other structures and means, but is not limited thereto.

According to the structure described above, the solution supply pipe 121 and the nozzles 111a are connected to each other, and the nozzle valve 126 is provided in the nozzle supply pipe 125, Of the plurality of nozzle valves 126 when supplying the polymer spinning solution to the respective nozzles 111a through the respective nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The polymer spinning solution is selectively discharged only from the nozzles 111a at specific positions among the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, Or a specific nozzle valve 126 is closed so that the nozzles 111a provided in the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, The nozzle tubular body 112a, the tubular body 112a, the tubular body 112a, and the nozzle body 112b are separated from the spinning liquid main tank 120 by the nozzle valve 126, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i, the supply of the polymer spinning solution supplied to each nozzle 111a is individually controlled and controlled.

In an embodiment of the present invention, the solution supply pipe 121 is provided with a supply valve 122 so that the nozzle tubes 112a, 112b, 112c, 112d and 112e of the nozzle block 111 in the spinning liquid main tank 120 112b, 112c, 112d, 112f, 112g, 112h, and 112i, and a nozzle valve 126 is provided in the nozzle supply pipe 125 to adjust the supply amount of the polymer solution, 112b, 112c, 112d, 112e, 112f, 112c, 112d, 112e, 112f, 112f, 112g, 112h, 112i to regulate and control the radiation amount of the polymer spinning solution which is radiated through each nozzle 111a, 112a, 112b, 112g, 112h, and 112i, the nano membranes having different weights in the longitudinal direction of the base material 115 are stacked by the polymer spinning solution electrospunning from the respective nozzles 111a of the nozzle blocks 111, 111a are arranged in the nozzle array 111a, the nozzles 111a are directly controlled and controlled individually The nanofibers having different basis weights may be laminated in the longitudinal direction of the base material 115 by controlling and controlling the amount of the spinning liquid to be electrospun through the respective nozzles 111a, but the present invention is not limited thereto.

The MD direction used in the present invention means a machine direction, and means a longitudinal direction corresponding to the progress direction in the case of continuous production of fibers such as a film or a nonwoven fabric, and the CD direction means a perpendicular direction to the CD direction as a cross direction . MD is the machine direction / longitudinal direction, and CD is the width direction / transverse direction.

Basis Weight or Grammage is defined as the mass per unit area, that is, the preferred unit, grams per square meter (often referred to as gsm rather than g / m2).

The basis weight should be measured in accordance with compendial methods, namely ASTM D 756, ISO 536 and EDANA ERT-40.3-90. The equipment required is scissors or die-cutters for sample cutting and precision weighing instruments (balances). The sample is cut to a total area per layer of 100 cm < 2 > with an accuracy of +/- 0.5%. A balance with a sensitivity of 0.001 g is required, which is read and adjusted to within 0.25% of the applied load and has such precision. The sample is conditioned to about 23 ° C. (± 2 ° C.) and about 50% relative humidity for about two hours to reach equilibrium. Weigh and record 10-fold cut samples from a sample area of a total of 1000 square centimeters, or 0.1 m2, on an analytical balance at approximately 0.001 g. (For samples thicker than 1 mm, it is advisable to weigh one layer only, but note if this is the case.) Divide the weight by the sample area (all tested layers) and calculate the basis weight to obtain gsm basis weight. All data are recorded for statistical analysis.

Hereinafter, the heat-resistant polymer used in the present invention will be described. The heat-resistant polymer of the present invention and polyvinylidene fluoride and polyamide are preferable.

First, the heat-resistant polymer may be at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or a composite composition thereof, a polyamide, a polyimide, a polyamideimide, a poly (meta-phenylene isophthalamide ), Meta-aramid, polyethylene chlorotrifluoroethylene, polychlorotrifluoroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polyvinylidene chloride-acrylonitrile copolymer, polyacrylamide, etc. . ≪ / RTI >

First, the polyamide used in the present invention will be described.

Polyamide refers to a generic term for a polymer linked by an amide bond (-CONH-), which can be obtained by condensation polymerization of a diamine and a dicarboxylic acid. Polyamides are characterized by amide bonds in the molecular structure, and their physical properties vary depending on the ratio of amide groups. For example, when the ratio of amide groups in the molecule is increased, specific gravity, melting point, absorbency, rigidity and the like are increased.

In addition, polyamide is a material used in a wide range of fields such as clothing, tire cord, carpet, rope, computer ribbon, parachute, plastic and adhesive due to its excellent resistance to corrosion, abrasion resistance, chemical resistance and insulation.

Generally, polyamides are classified into aromatic polyamides and aliphatic polyamides. Representative aliphatic polyamides include nylon. Nylon is originally a trademark of DuPont, Inc., but is now used as a generic name.

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

First, nylon 6 is characterized by excellent heat resistance, moldability and chemical resistance, and is produced by ring-opening polymerization of ε-caprolactam in order to produce it. Nylon 6 means that caprolactam has 6 carbon atoms.

(Scheme 1) Nylon 6 polymerization of caprolactam

On the other hand, nylon 66 is generally similar in properties to nylon 6, but is superior in heat resistance to nylon 6 and superior in self-extinguishing and abrasion resistance. Nylon 66 is prepared by dehydration condensation polymerization of hexamethylenediamine and adipic acid.

(Scheme 2) Dehydration condensation of hexamethylenediamine with adipic acid Nylon 66 polymerization by polymerization

Nylon 46 is also excellent in heat resistance, mechanical properties and impact resistance, and has a high processing temperature. Nylon 46 is prepared by polycondensation of tetramethylenediamine and adipic acid. Diaminobutane (DAB), a raw material, is prepared from the reaction of acrylonitrile with hydrogen cyanide. In the first stage of the polymerization operation, a salt is formed from diaminobutane and adipic acid, and the mixture is polymerized under appropriate pressure The prepolymer is converted into a prepolymer and the solid of the prepolymer is polymerized at a solid state by treatment at about 250 ° C in the presence of nitrogen and water vapor.

Nylon 46, in particular, is characterized by a high amide concentration and a regular arrangement between the 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.

The present invention provides a mask comprising nanofibers having different basis weights in the MD direction on a substrate using the polyamide, and a method for producing the same.

More specifically, first, a polyamide solution in which polyamide is dissolved in an organic solvent is supplied to a spinning liquid main tank 8 connected to the unit 110 of the electrospinning device, and the polyamide solution supplied to the spinning solution main tank 8 The solution is continuously supplied in a constant amount 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 polyamide solution supplied from each of the nozzles 12 is electrospun and converged on a substrate placed on the collector 13 having a high voltage through the nozzle 12 to laminate the polyamide nanofibers.

After the polyamide nanofibers are laminated in the unit 110 by the above-described method, in the lapping apparatus 100 located at the rear end of the electrospinning device 1, another substrate is a laminate of the polyamide nano- It is possible to manufacture the mask through a process of being bonded to one side of the base material and heat-sealed in the laminating device 90. [

The polyvinylidene fluoride used in the present invention will now be described. The polyvinylidene fluoride (PVDF) resin is one of the fluoro-based polymers, and the fluororesin contains fluorine, which is excellent in thermal and chemical properties. In producing a spinning solution in which polyvinylidene fluoride is dissolved in an appropriate organic solvent, the polyvinylidene fluoride includes a homopolymer of vinylidene fluoride or a copolymerized polymer containing vinylidene fluoride in a molar ratio of 50% or more , A homopolymer is more preferable from the viewpoint of excellent strength of the polyvinylidene fluoride resin. When the polyvinylidene fluoride resin is a copolymer polymer, known copolymerizable monomers copolymerized with vinylidene fluoride monomers may be suitably used For example, fluorine-based monomers and chlorine-based monomers can be suitably used.

The weight average molecular weight (Mw) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 500,000, and when the weight average molecular weight of the polyvinylidene fluoride resin is less than 10,000, The fibers can not obtain sufficient strength. When the number average molecular weight exceeds 500,000, the handling of the solution is not easy, and the processability is deteriorated, making it difficult to obtain uniform nanofibers. The present invention provides a nanomembrane having different basis weights in the MD direction on a substrate using the polyvinylidene fluoride and a method for producing the same.

Among the heat-resistant polymers to be used in the present invention, polyacrylonitrile may be preferably used.

Generally, polyacrylonitrile (PAN) refers to a polymer of acrylonitrile (CH2 = CHCN).

(Reaction formula 3) The unit of polyacrylonitrile

Here, the polyacrylonitrile resin is a copolymer made from a mixture of acrylonitrile and a monomer constituting the majority. Frequently used monomers include butadiene styrene vinylidene chloride or other vinyl compounds. The acrylic fiber contains at least 85% acrylonitrile, and the mode acrylic contains 35 to 85% acrylonitrile. When other monomers are included, the fiber has the property of increasing the affinity to the dye. More specifically, in the production of an acrylonitrile-based copolymer and spinning solution, in the case of producing an acrylonitrile-based copolymer, there is little contamination of nozzles in the course of manufacturing ultrafine fibers by electrospinning, Thereby increasing the solubility in the solvent and imparting better mechanical properties. In addition, polyacrylonitrile has a softening point of 300 ° C or more and is excellent in heat resistance.

The degree of polymerization of the polyacrylonitrile is preferably 1,000 to 1,000,000, and more preferably 2,000 to 1,000,000.

The polyacrylonitrile is preferably used within a range that satisfies the usage amount of the acrylonitrile monomer, the hydrophobic monomer and the hydrophilic monomer. When the polymer is polymerized, the weight% of the acrylonitrile monomer is too low to be electrospun when the weight% of the hydrophilic monomer and the weight% of the hydrophobic monomer are 3: 4 and the total monomer is less than 60, It is difficult to form a stable jet (JET) at the time of electrospinning as well as to cause contamination of the nozzle. If the ratio is more than 99, the spinning viscosity is too high to spin, and even if an additive capable of lowering the viscosity is added, the diameter of the microfine fibers becomes too large and the productivity of electrospray is too low to achieve the object of the present invention.

In addition, as much amount of comonomer is added to the acrylic polymer, the amount of the crosslinking agent must be increased so that the stability of electrospinning can be secured and deterioration of the mechanical properties of the nanofiber can be prevented.

The hydrophobic monomer may be an ethylene-based compound such as methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl pyrrolidone, vinylidene chloride or vinyl chloride, It is preferable to use at least one selected.

Wherein the hydrophilic monomer is selected from the group consisting of acrylic acid, allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, butanediol monoacrylate, dimethylaminoethyl acrylate, butent ricarboxylic acid, vinyl It is preferable to use at least one selected from ethylene-based compounds such as sulfonic acid, allylsulfonic acid, methallylsulfonic acid, and para-styrenesulfonic acid and polyvalent acids or derivatives thereof.

As the initiator to be used for preparing the acrylonitrile-based polymer, an azo-based compound or a sulfate compound may be used, but it is generally preferable to use a radical initiator used for the oxidation-reduction reaction.

Among the heat-resistant polymers used in the present invention, polyethersulfone can also be preferably used.

In general, polyethersulfone (PES) is an amber transparent, amorphous resin having the following repeating unit, and is generally produced by condensation polymerization of dichlorodiphenylsulfone.

(Reaction formula 4) The unit of polyether sulfone

Polyethersulfone is a super heat resistant engineering plastic developed by ICI in the UK. It is a highly heat resistant polymer among thermoplastic plastics. Since the polyethersulfone is amorphous, the physical properties of the polyether sulfone are not lowered by temperature rise, and the temperature dependency of the flexural modulus is small, so that it hardly changes at -100 to 200 캜. The load-strain temperature is 200 to 220 占 폚, and the glass transition temperature is 225 占 폚. In addition, the creep resistance up to 180 占 폚 is the most excellent among the thermoplastic resins, and has the characteristic of being resistant to hot water and steam at 150 to 160 占 폚.

Due to such characteristics, polyethersulfone is used in optical disks, magnetic disks, electric and electronic fields, hydrothermal fields, automobile fields, and heat resistant paints.

Examples of the solvent usable with the polyethersulfone include acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide (DMF), dimethylacetamide (DMAc), N- N-methyl pyrrolidone (NMP), cyclohexane, water, or a mixture thereof, but the present invention is not limited thereto.

On the other hand, the mask according to the present invention comprises a first substrate; A first adhesive layer formed on the first substrate; A nanofiber layer formed on the adhesive layer; A second adhesive layer formed on the nano fiber layer; And a second substrate formed on the second adhesive layer.

The adhesive layer may comprise a low melting point polymer or an epoxy resin-curing agent.

Here, the low-melting-point polymer may be a low-melting-point polyurethane, a low-melting-point polyester, or a low-melting polyvinylidene fluoride, alone or in combination of two or more.

The low-melting-point polyurethane uses a low-polymerization polyurethane having a softening temperature of 80-100 ° C.

The low melting point polyester is preferably terephthalic acid, isophthalic acid or a mixture thereof. It is also possible to add ethylene glycol as a diol component to further lower the melting point.

The low melting point polyvinylidene fluoride is a low melting point polyvinylidene fluoride having a weight average molecular weight of 5,000 and a melting point of 80 to 160 ° C.

In the present invention, an epoxy resin-curing agent solution can be used in forming the adhesive layer.

At this time, the epoxy resin is an intermediate of a thermosetting resin and forms a three-dimensional network structure insoluble / infusible by reaction with a curing agent to exhibit physical properties inherent to epoxy, and the epoxy resin is adhered It has an advantage of being excellent in properties, mechanical strength, heat resistance, chemical resistance, water resistance, electric insulation property, moldability and impregnation property, easy production of a composite material, and realizing various properties according to the selection of a curing agent.

Nonlimiting examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.

The above-mentioned bisphenol A type epoxy resin is represented by the following general formula (1), and the most commonly used epoxy resin is produced by a direct method or indirect method.

[Chemical Formula 1]

The bisphenol F type epoxy resin is represented by the following general formula (2) and is produced by the reaction of bisphenol F with ECH. The bisphenol F type epoxy resin has a lower viscosity than the bisphenol A type epoxy resin and theoretically has a somewhat lower mechanical and physical properties. And the like.

(2)

The bisphenol S type epoxy resin is represented by the following general formula (3), and is generally used for rapidly curing an epoxy adhesive and used as a reactant in a polymer reaction.

(3)

On the other hand, the curing agent is preferably one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent, but is not limited thereto.

Non-limiting examples of the amine-based curing agent include aliphatic polyamines, modified aliphatic polyamines, aromatic amines, tertiary amines, and secondary amines.

Examples of the aliphatic polyamines include diethylene triamine (DETA), triethylene tetramine (TETA), diethylamino propyl amine (DEAPA), Menthane diamine (MDA), N-aminoethyl piperazine Isophorone diamine (IPDA), but is not limited thereto.

Examples of the modified aliphatic polyamines include, but are not limited to, Epoxy Polyamine Adduct, Ethylene or Propylene Oxide, Polyamine adduct, Cyanoethylated Polyamine, and Ketone blocked Polyamine (Ketimine).

Examples of the aromatic amine include, but are not limited to, Meta phenylene Diamine (MPD), 4.4 'Dimethyl aniline (DAM or DDM), Diamino Diphenyl Sulfone (DDS), and Aromatic amine adduct.

Examples of the acid anhydride-based curing agent include polyamide (PA), tetrahydrophthalic anhydride (THPA), methyl tetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), and MNA.

Nonlimiting examples of the imidazole-based curing agent include 2MZ and 2E4MZ.

In addition, the curing agent solution may further include a curing accelerator.

The curing accelerator used in the present invention is not particularly limited as long as it is a curing accelerator generally used for accelerating the curing of the epoxy compound and includes, for example, tertiary amines, tertiary amine salts, imidazoles, Quaternary ammonium salts, quaternary phosphonium salts, organic metal salts, and boron compounds. The curing accelerator may be used alone or in combination of two or more.

Examples of tertiary amines include lauryldimethylamino, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, (N, N- dimethylaminomethyl) (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] 5 (DBN).

Examples of the tertiary amine salt include a carboxylate, a sulfonate, and an inorganic acid salt of the above-mentioned tertiary amine. Examples of the carboxylate include salts of carboxylic acids having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylate (particularly fatty acid salts). Examples of the sulfonic acid salt include p-toluenesulfonic acid salt, benzenesulfonic acid salt, methanesulfonic acid salt and ethanesulfonic acid salt. Representative examples of tertiary amine salts include salts of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (for example, p-toluenesulfonic acid salt and octylic acid salt).

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, stannous stearate and zinc stearate. As the metal-based curing accelerator, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility And particularly, cobalt (II) acetylacetonate and zinc naphthenate are preferable. The metal-based curing accelerator may be used singly or in combination of two or more.

 The addition amount of the metal-based curing accelerator is preferably in the range of from 25 to 500 ppm, more preferably from 40 to 200 ppm, of the metal based on the metal-based curing accelerator when the non-volatile content in the resin composition is 100 mass% . If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low roughness with good adhesion to the surface of the insulating layer. When it exceeds 500 ppm, the storage stability and insulating property of the resin composition tend to be lowered.

Examples of the quaternary ammonium salt include tetraethylammonium bromide and tetrabutylammonium bromide.

 As the quaternary phosphonium salt, for example, the following formula (1)

(Wherein R1, R2, R3 and R4 are the same or different and each represents a hydrocarbon group of 1 to 16 carbon atoms, and X represents an anion residue of a carboxylic acid or an organic sulfonic acid).

 Examples of the hydrocarbon group having 1 to 16 carbon atoms include a linear or branched hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, A straight chain alkyl group; Vinyl, allyl, crotyl group, etc.

A straight chain or branched alkenyl group; Aryl groups such as phenyl, toluyl, xylyl, naphthyl, anthryl, phenanthryl groups; And aralkyl groups such as benzyl and phenethyl groups. Of these, a straight or branched alkyl group having 1 to 6 carbon atoms, particularly a butyl group, is preferred.

 Examples of the "carboxylic acid" in the "anion residue of a carboxylic acid or an organic sulfonic acid" include aliphatic alcohols having 1 to 20 carbon atoms such as octanoic acid, decanoic acid, lauric acid, myristic acid and palmitic acid Monocarboxylic acids; 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylate Alicyclic carboxylic acids (monocyclic alicyclic mono- or polycarboxylic acids, crosslinked cyclic mono- or polycarboxylic acids), and the like. The alicyclic carboxylic acid may have a substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, or a halogen atom such as a chlorine atom It is possible. As the carboxylic acid, an aliphatic monocarboxylic acid having a carbon number of 10 to 18 and an alicyclic polycarboxylic acid having a carbon number of 8 to 18 are preferable.

Examples of the "organic sulfonic acid" in the above "anionic residue of a carboxylic acid or an organic sulfonic acid" include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, Aliphatic sulfonic acids such as 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecane sulfonic acid (for example, an aliphatic sulfonic acid having 1 to 16 carbon atoms); Benzene sulfonic acid, 3- (linear or branched octadecyl) benzene sulfonic acid, 4- (straight or branched octyl) benzenesulfonic acid, 3- (linear or branched dodecyl) benzene sulfonic acid, p-toluene sulfonic acid, Benzenesulfonic acid, 4-methoxybenzenesulfonic acid, 4-ethoxybenzenesulfonic acid, 4- (4-methoxybenzenesulfonic acid), 4- Chlorobenzene sulfonic acid, and the like.

Representative examples of quaternary phosphonium salts include tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, tetrabutylphosphonium myristate, tetrabutylphosphoniumpolate, tetrabutylphosphonium cation and bicyclo [2.2 .1] heptane-2,3-dicarboxylic acid and / or methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, a salt of an anion of tetrabutylphosphonium cation with 1,2,4 , Salts of anions of 5-cyclohexanetetracarboxylic acid, salts of anions of tetrabutylphosphonium cation and methanesulfonic acid, salts of anions of tetrabutylphosphonium cation and benzenesulfonic acid, salts of tetrabutylphosphonium cation and p-toluenesulfonic acid Salts of anions of tetrabutylphosphonium cation and 4-chlorobenzenesulfonic acid, salts of anions of tetrabutylphosphonium cation and dodecylbenzenesulfonic acid, and the like.

Examples of the boron compound include boron trifluoride, triphenylborate, and the like.

 Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- , 4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine isocyanuric acid adduct, Methyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Imidazole compounds such as pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, And adducts of a thiol compound with an epoxy resin.

 Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like.

Hereinafter, a method of manufacturing a mask including an adhesive layer will be described.

The low-melting-point polymer unit or the epoxy resin-curing agent unit and the spinning solution unit have a main tank 8 in which a low melting point polymer, an epoxy resin-curing agent or a polymer spinning solution is filled, (Not shown) for supplying a low-melting-point polymer, an epoxy resin-curing agent or a polymer spinning solution in a fixed amount, and a low melting point polymer, an epoxy resin-curing agent or a polymer spinning solution filled in the main tank 8, A nozzle block 11 in which a plurality of nozzles 12 in a pin shape are arranged and a collector 13 spaced from the nozzle 12 by a predetermined distance in order to accumulate spinning liquid sprayed from the nozzle 12, (14a, 14b, 14c) for generating a voltage in the capacitor (13). (14c is not shown)

According to the structure as described above, the electrospinning device 1 according to the present invention is characterized in that the low melting point polymer, the epoxy resin-curing agent, or the polymer spinning liquid filled in the main tank 8 is formed in the nozzle block 11 through the metering pump An epoxy resin-curing agent or a polymer spinning solution is radiated and focused on a collector 13 with a high voltage applied thereto through a nozzle 12, and the low-melting-point polymer, A nanofiber nonwoven fabric is formed on the long sheet 15 moved on the collector 13, and the formed nanofiber nonwoven fabric is made of a nanomask.

In this case, a feed roller 3 (not shown) for feeding a long sheet 15 on which a nanofiber nonwoven fabric is laminated by spraying a polymer spinning solution is provided in front of the low melting point polymer unit or the epoxy resin-curing agent unit of the electrospinning device 1 And a winding roller 5 for winding up a long sheet 15 on which a nanofiber nonwoven fabric is laminated is provided at the rear of the unit located at the rear end.

On the other hand, it is preferable that the elongated sheet 15, in which the polymer solution is laminated while passing through the low melting point polymer unit or the epoxy resin-curing agent unit and the spinning solution unit, is made of nonwoven fabric or fabric.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example 1

A spinning solution having a concentration of 15% by weight prepared by dissolving polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 in dimethylacetamide (N, N-dimethylacetamide, DMAc) was prepared. The polyvinylidene fluoride solution was put into the spinning liquid main tank, and the nozzle block including the on-off system designed to separate the nozzle block in the MD direction was applied with an applied voltage of 20 kV. Polyvinylidene fluoride having a basis weight of 3 g / The rid nanofibers were electrospun on a substrate. The nanofibers electrospun on the substrate had a vertical width of 180 cm in the MD direction, alternately 20 cm of polyvinylidene fluoride nanofiber had a basis weight of 2 g / m 2, and 5 cm of polyvinylidene fluoride nanofiber Polyvinylidene fluoride nanofibers including a structure in which the basis weight was repeatedly 7 g / m < 2 > were formed, and polyvinylidene fluoride nanofibers having different weights of nanofibers in the MD direction were formed. At this time, bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C. Thereafter, another substrate was bonded to one side of the substrate on which the nylon 6 nanofibers were not laminated, and the substrate was thermally fused in a laminating apparatus to prepare a mask.

Example 2

A spinning solution having a concentration of 15% by weight prepared by dissolving polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 in dimethylacetamide (N, N-dimethylacetamide, DMAc) was prepared. The polyvinylidene fluoride solution was put into the spinning liquid main tank, and the nozzle block including the on-off system designed to separate the nozzle block in the MD direction was applied with an applied voltage of 20 kV. Polyvinylidene fluoride having a basis weight of 3 g / The rid nanofibers were electrospun on a substrate. The nanofibers electrospun on the substrate had a vertical width of 180 cm with respect to the MD direction, alternately 20 cm of the polyvinylidene fluoride nanofiber had a basis weight of 1 g / m 2, and 5 cm of the polyvinylidene fluoride nanofiber The polyvinylidene fluoride nanofiber including the structure in which the basis weight was repeatedly 8 g / m < 2 > was formed, and the polyvinylidene fluoride nanofiber having the different basis weight of the nanofibers in the MD direction was formed. At this time, bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C. Thereafter, another substrate was bonded to one side of the substrate on which the nylon 6 nanofibers were not laminated, and the substrate was thermally fused in a laminating apparatus to prepare a mask.

Example 3

A spinning solution having a concentration of 15% by weight prepared by dissolving polyvinylidene fluoride having a weight average molecular weight (Mw) of 50,000 in dimethylacetamide (N, N-dimethylacetamide, DMAc) was prepared. The polyvinylidene fluoride solution was put into the spinning liquid main tank, and the nozzle block including the on-off system designed to separate the nozzle block in the MD direction was applied with an applied voltage of 20 kV. Polyvinylidene fluoride having a basis weight of 3 g / The rid nanofibers were electrospun on a substrate. The nanofibers electrospun on the substrate had a vertical width of 180 cm with respect to the MD direction, alternately 20 cm of the polyvinylidene fluoride nanofiber had a basis weight of 3 g / m 2, and 5 cm of the polyvinylidene fluoride nanofiber The polyvinylidene fluoride nanofiber including the structure in which the basis weight was repeatedly 6 g / m < 2 > was formed, and the polyvinylidene fluoride nanofiber having the different basis weight of the nanofibers in the MD direction was formed. At this time, bottom-up electrospinning was performed under the condition that the distance between the electrode and the collector was 40 cm and the temperature was 22 ° C. Thereafter, another substrate was bonded to one side of the substrate on which the nylon 6 nanofibers were not laminated, and the substrate was thermally fused in a laminating apparatus to prepare a mask.

Example 4

Electrospinning was carried out in the same manner as in Example 1 except that nylon was replaced with nylon solution in which nylon was dissolved in a solvent of dimethylacetamide (DMAc) instead of polyvinylidene fluoride solution.

Example 5

Electrospinning was carried out in the same manner as in Example 2 except that nylon was replaced with a nylon solution in which nylon was dissolved in a solvent of dimethylacetamide (DMAc) instead of polyvinylidene fluoride solution.

Example 6

Electrospinning was carried out in the same manner as in Example 3, except that nylon was replaced with nylon solution in which nylon was dissolved in a solvent of dimethylacetamide (DMAc) instead of polyvinylidene fluoride solution.

100: electrospinning device 110, 110 ': unit
111: nozzle block 111a: nozzle
112: nozzle tube body
112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
113: collector 114: voltage generating device
115: substrate 115a, 115b, 115c: nanofiber
116a: conveying belt 116b: conveying roller
120: spinning liquid main tank 121: solution supply pipe
122: supply valve 125: nozzle supply pipe
126: Nozzle valve
a, b, c, d: Nanofibers having different weights in the MD direction

Claims (5)

A method of manufacturing a mask using bottom-up electrospinning, the method comprising: fabricating a bottom-up electrospinning device including a plurality of nozzle tubes in a bottom-
Wherein the weight of the nanofibers in the MD direction is different from that of the nanofibers in the MD direction by controlling the basis weight of the nanofibers by operating the plurality of nozzle tubes with an on-off system. delete The method according to claim 1,
Wherein the on-off system is designed such that the basis weight of the nanofibers is alternately changed in the MD direction in which the nanofibers are integrated. The method according to claim 1,
The on-off system is designed such that the basis weight is alternately shifted in the MD direction in which the nanofibers are integrated, and the alternation period in which the basis weight is designed is 30 to 80 cm in which the basis weight of the nanofibers is 1 to 6 g / Wherein the basis weight of the nanofibers in the MD direction is in the range of 5 to 30 cm. A process for producing a polyurethane foam, which is produced by the production method of any one of claims 1, 3 and 4,
A first substrate; A nanofiber formed on the first base material and different in basis weight in the MD direction; And a second substrate formed on the nanofibers.

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