KR101778250B1 - Filter including polyvinylidene fluoride nanofiber having multiple fiber-diameter group with low melting point polymer adhension layer and its manufacturing method - Google Patents

Filter including polyvinylidene fluoride nanofiber having multiple fiber-diameter group with low melting point polymer adhension layer and its manufacturing method Download PDF

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KR101778250B1
KR101778250B1 KR1020150057474A KR20150057474A KR101778250B1 KR 101778250 B1 KR101778250 B1 KR 101778250B1 KR 1020150057474 A KR1020150057474 A KR 1020150057474A KR 20150057474 A KR20150057474 A KR 20150057474A KR 101778250 B1 KR101778250 B1 KR 101778250B1
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melting point
low melting
nanofiber
filter
nozzle
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KR1020150057474A
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Korean (ko)
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KR20160126462A (en
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박종철
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(주)에프티이앤이
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Priority to KR1020150057474A priority Critical patent/KR101778250B1/en
Priority to PCT/KR2015/007142 priority patent/WO2016171328A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4358—Polyurethanes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
    • F02C7/04—Air intakes for gas-turbine plants or jet-propulsion plants
    • F02C7/05—Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles
    • F02C7/052—Air intakes for gas-turbine plants or jet-propulsion plants having provisions for obviating the penetration of damaging objects or particles with dust-separation devices

Abstract

The present invention relates to a filter including nanofibers and a method of manufacturing the same. The filter includes a substrate having a first polyvinylidene fluoride nanofiber layer having a fiber diameter of 150 to 300 nm and a second polyvinylidene fluoride nanofiber layer having a fiber diameter of 100 to 150 nm. Wherein the adhesive layer is formed by laminating and forming the vinylidene fluoride nanofiber layer, wherein the adhesive layer is formed by electrospinning the low melting point polymer between the substrate, the nanofiber layer, and the nanofiber layer.
The nanofiber filter according to the present invention is advantageous in that it is not only easily dislodged but also can be continuously produced, and thus the process efficiency is excellent and mass production is advantageous.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a filter including polyvinylidene fluoride nanofibers having different diameters and having a low melting point polymer adhesive layer,

The present invention relates to a filter including nanofibers and a method of manufacturing the same. The filter includes a substrate having a first polyvinylidene fluoride nanofiber layer having a fiber diameter of 150 to 300 nm and a second polyvinylidene fluoride nanofiber layer having a fiber diameter of 100 to 150 nm. The present invention relates to a nanofiber filter and a method for fabricating the nanofiber filter. The nanofiber filter is characterized in that the nanofiber layer and the vinylidene fluoride nanofiber layer are laminated and adhered to each other with an adhesive layer formed by electrospinning a low melting point polymer between the substrate, the nanofiber layer and the nanofiber layer.

Generally, a filter is classified as a liquid filter and an air filter as a filtration device for filtering foreign matters in a fluid. Among these, the air filter has been developed in order to prevent the defects of high-tech products with the development of high-tech industries, and to manufacture semiconductor devices, assemblies of computers, hospitals, It is used in food processing factories, agriculture and forestry fisheries field, and is widely used in dusty workshop and thermal power plant. A gas turbine used in a thermal power plant sucks compressed air from the outside and compresses it, then injects the compressed air into the combustor together with the fuel, mixes the mixed air and fuel, and burns the high temperature and high pressure combustion gas And is then injected into the vanes of the turbine to obtain rotational power. Because these gas turbines are made up of very precise parts, they are periodically serviced and use air filters for pretreatment to purify the air in the air entering the compressor.

 The air filter is capable of supplying purified air by preventing foreign substances such as dust and dust contained in the air from permeating into the filter filter material when the combustion air sucked into the gas turbine is taken in the air. However, particles having a large particle size accumulate on the surface of the filter media, forming not only a filter cake on the surface of the filter media, but also accumulating fine particles in the filter media, thereby blocking the pores of the filter media. As a result, when the particles are accumulated on the surface of the filter media, there is a problem of increasing the pressure loss of the filter and decreasing the service life.

 On the other hand, in the conventional air filter, the principle that the static electricity is applied to the fibrous aggregate constituting the filter medium to collect the particles by the electrostatic force is used, and the efficiency of the filter by the above principle has been measured. However, the European air filter classification standard EN779 recently decided to exclude the filter efficiency due to the electrostatic effect in 2012. As a result of measuring the efficiency by excluding the electrostatic effect, the actual efficiency of the filter is lowered by more than 20% It turned out.

 In order to solve the above-mentioned problems, various methods of manufacturing nano-sized fibers and applying them to filters have been developed and used. When nanofibers are applied to a filter, the specific surface area is larger than that of a conventional filter material having a large diameter, and the flexibility of the surface functional group is also good. In addition, by having the processing size of nano gold, it is possible to efficiently filter fine dust particles.

In addition, in the case of a technique for spinning conventional 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. Conventional electrospinning devices produce nanofibers by layering a nanofiber web by electrospinning a spinning solution on one side of a substrate supplied from the outside. That is, the conventional electrospinning device is composed of a bottom-up or top-down electrospinning device, and electrospun spinning solution is applied only to the lower surface or the upper surface of the substrate supplied into the electrospinning device to form a nanofiber web.

As described above, since the electrospinning device is composed of the bottom-up electrospinning device or the top-down electrospinning device, the spinning solution is electrospun on the lower surface or the upper surface of the base material supplied from the outside and conveyed in a predetermined direction, The nanofiber or nanofiber filter formed can be produced.

However, when the polymeric spinning solution is electrospun on the substrate through the bottom-up electrospinning device or the top-down electrospinning device to form a laminate of nanofiber webs, the nanofiber web may be removed from the substrate during transfer of the substrate, There is a problem that the nanofiber web is dislodged from the substrate of a product made of a fiber filter.

That is, when the nanofiber web is laminated by electrospinning the polymer spinning solution on the base material through the electrospinning device, the product made of the nanofiber or the nanofiber filter is used as the material of the base and the polymer spinning solution The nanofiber web on which the polymer spinning solution is electrospun and laminated is desorbed from the substrate due to the difference in the composition.

Meanwhile, a laminating process for laminating the base material and the nanofiber web to be pressed in the nanofiber or nanofiber filter manufactured through the electrospinning device is provided as a post-process. However, since the material and the composition of the base and the polymer solution are different The nanofiber web on which the polymer spinning solution is electrospun and laminated is desorbed from the substrate.

In order to solve the problems described above, the polymer spinning solution and the hot melt are mixed and supplied to the nozzle block of the electrospinning device when the polymer spinning solution is supplied, so that the polymer spinning solution is injected simultaneously with the polymer spinning solution during the electrospinning of the polymer spinning solution It has been proposed to prevent desorption of a nanofiber web on which a substrate and a polymer spinning solution are electrospun by a hot melt. However, in the case of mixing a polymer spinning solution and a hot melt, a polymer spinning solution There is a problem that the hot melt is radiated to the portion and the portion where the hot melt is not required, thereby deteriorating the performance and quality of the nanofiber or nanofiber filter.

Further, the use amount of the hot melt is increased by mixing hot melt in the polymer spinning solution, and the performance and quality of the nanofiber web, which is laminated by electrospinning of the polymer spinning solution on the substrate upon mixing and adding an excessive amount of hot melt to the polymer spinning solution And the like.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, A first nanofiber layer of polyvinylidene fluoride having a fiber diameter of 100 to 150 nm; And a polyvinylidene fluoride second nanofiber layer having a fiber diameter of 80 to 150 nm, wherein the adhesion between the substrate and the first nanofiber layer and between the first nanofiber layer and the second nanofiber layer is achieved by electrospinning the low melting point polymer solution The present invention also provides a nanofiber filter comprising the nanofiber filter.

It is another object of the present invention to provide a filter manufactured by introducing a unit concept into an electrospinning apparatus, which can be mass-produced and has a uniform quality.

In order to solve the above problems,

A substrate;

A first nanofiber layer of polyvinylidene fluoride having a fiber diameter of 100 to 150 nm; And

A second polyvinylidene fluoride nanofiber layer having a fiber diameter of 80 to 150 nm;

Wherein the adhesion between the base material and the first nanofiber layer, between the first nanofiber layer and the second nanofiber layer is adhered through an adhesive layer formed by electrospinning the low melting point polymer solution. As a means for.

The low-melting-point polymer solution used in the present invention may be selected from low-melting-point polyesters, low-melting-point polyurethanes and low-melting-point polyvinylidene fluorides, And may be electrospun on the whole or a part of the second nanofiber layer.

The polyvinylidene fluoride solution for forming the first and second nano fiber layers is maintained at a viscosity of 1,000 cps to 3,000 cps through a temperature controller.

The nanofiber filter manufactured by the present invention is easier to adhere between the base layer and the polymer electrospinning layer than the conventional filter and is not easily separated, and is sprayed only on specific regions and portions on the substrate, And at the same time minimize the interference of the low melting point polymer with respect to the nanofiber layer, thereby improving the performance and quality of the nanofiber or nanofiber filter.

Also, the filter manufactured by the method can reduce the pressure loss, increase the filtration efficiency, and extend the life of the filter.

1 is a side view schematically showing an electrospinning apparatus according to the present invention,
2 is a side sectional view schematically showing a nozzle of a nozzle block installed in a unit of the electrospinning apparatus according to the present invention,
3 is a schematic view of a nozzle block installed in a spinning liquid unit of an electrospinning device according to the present invention,
4 is a perspective view schematically showing a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention,
5 is a sectional view taken along the line A-A 'in FIG. 4,
6 is a perspective view schematically showing a nozzle block installed in a low melting point polymer unit of an electrospinning device according to the present invention,
FIG. 7 to FIG. 10 are plan views schematically illustrating an operation process of electrospinning a polymer spinning solution on the same plane of a substrate through nozzles of each nozzle tube of an electrospinning device for manufacturing a nanofiber web according to the present invention. FIG.
FIGS. 11 and 12 are plan views schematically illustrating an operation process of sequentially injecting a low melting point polymer and a polymer spinning solution through arrangement of a nozzle block in the low melting point polymer unit as shown in FIG. 6,
13 is a view showing a state in which the nozzle blocks provided in the low melting point polymer unit of the electrospinning apparatus according to the present invention are arranged in different shapes,
FIGS. 14 and 15 are diagrams illustrating an operation process of sequentially injecting a low-melting-point polymer and a polymer spinning solution according to the arrangement of the nozzles as shown in FIG. 13;
16 is a view showing a state in which the nozzle blocks provided in the low melting point polymer unit of the electrospinning apparatus according to the present invention are arranged in another form,
FIGS. 17 and 18 are diagrams showing an operation process in which the low melting point polymer and the polymer spinning solution are sequentially injected according to the arrangement of the same nozzle as shown in FIG. 16;
19 is a front view showing a laminated structure of the nanofiber filter manufactured by the present invention.

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 spirit of the present invention.

1 is a side view schematically showing an electrospinning apparatus according to the present invention. The electrospinning apparatus 1 according to the present invention comprises a bottom-up electrospinning apparatus 1, wherein at least one low-melting polymer unit 10a, 10c and a spinning liquid unit 10b, The low melting point polymer units 10a and 10c and the spinning solution units 10b and 10d are separately electrospinning the low melting point polymer or the polymer spinning solution, .

The low melting point polymer units 10a and 10c electrospun a low melting point polymer solution for forming an adhesive layer and the spinning solution units 10b and 10d electrospun the polymer solution for forming a nanofiber layer.

The low melting point polymer solution electrospun in the low melting point polymer units (10a, 10c) is electrospun to form an adhesive layer to enhance adhesion between the substrate, the nano fiber layer, and the nano fiber layer, and to prevent desorption.

The low melting point polymer solution electrospun in the low melting point polymer units 10a and 10c is characterized by being a low melting point polyester, a low melting point polyurethane, and a low melting point polyvinylidene fluoride. This will be described later.

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

The low-melting-point polymer unit and spinning solution unit may include a main tank 8 in which a low-melting-point polymer or a polymer solution is filled, and a low-melting-point polymer or polymer solution filled in the main tank 8 in a predetermined amount A nozzle block 11 in which a plurality of nozzles 12 in the form of pins are arranged and installed is provided for discharging a low melting point polymer or polymer solution for use in filling the main tank 8 with a metering pump (not shown) And a voltage generator 14a, 14b, 14c, and 14c for generating a voltage to the collector 13, a collector 13 spaced apart from the nozzle 12 by a predetermined distance in order to accumulate the polymer spinning solution injected from the nozzle 12, 14d). (14c and 14d are not shown)

The electrospinning device 1 according to the present invention has a structure in which a low melting point polymer or a polymer spinning liquid filled in the main tank 8 is supplied to a plurality of nozzles (not shown) formed in the nozzle block 11 through a metering pump 12 and the supplied low melting point polymer or polymer spinning liquid is radiated and focused on a collector 13 having a high voltage applied thereto through a nozzle 12 to be transported on the collector 13 15), and the formed nanofiber layer is made of a filter.

2, the nozzle 12 provided in the nozzle block 11 of the electrospinning device 1 according to the present invention comprises a multi-tubular nozzle 500, And two or more inner and outer tubes 501 and 502 are combined in a sheath-core form so that the use solution can be electrospun at the same time.

The nozzle block 11 includes a nozzle plate 405 in which a sheath-core type multi-tubular nozzle 500 is arranged and a multi-tubular nozzle 500 positioned at a lower end of the nozzle plate 405 (Not shown) for supplying a polymer solution (not shown) to the overflow removing nozzles 415 and the overflow removing nozzles 415 surrounding the multi-tubular nozzles 500, The overflow liquid temporary storage plate 410 and the overflow liquid temporary storage plate 410 located at the upper right end of the nozzle plate 405 and the overflow removing nozzle 415 And an overflow removing nozzle support plate 416 for supporting the overflow removing nozzle 416.

An air supply nozzle 404 surrounding the multi-tubular nozzle 500 and the overflow removing nozzles 415 and an air supply nozzle 404 located at the uppermost end of the nozzle block 11 to support the air supply nozzle 404 An air inlet 413 located at the lower end of the support plate 414 of the supply nozzle and directly below the support plate 414 of the air supply nozzle for supplying air to the air supply nozzle 404 and an air storage 413 for storing the supplied air And a plate 411.

3 schematically shows a nozzle block installed in a spinning liquid unit of an electrospinning apparatus according to the present invention. As shown in the figure, a temperature regulating device 60 is installed in the tubular body 40 of the nozzle block 11, which is installed in each of the units, and in which a polymer solution is supplied to a plurality of nozzles 12 provided on the unit do.

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

The polymer spinning solution supplied to each tube 40 is discharged and injected through a plurality of nozzles 12 and accumulated on the long sheet 15 in the form of nanofibers.

A plurality of nozzles 12 are mounted at predetermined intervals in the longitudinal direction on each of the tubes 40. The nozzles 12 and the tubes 40 are electrically connected to the tube 40 .

In order to control the temperature control of the polymer solution, the temperature control device 60 is formed of a heat ray 41 or a pipe provided at the periphery of the tube 40.

Fig. 4 is a perspective view schematically showing a state in which an electric heater is installed in a nozzle block installed in each unit of the electrospinning apparatus according to the present invention, and Fig. 5 is a sectional view taken along the line A-A 'in Fig. As shown in the figure, a thermostat device in the form of a heat line 41 is formed in a spiral shape on the periphery of the tubular body 40 of the nozzle block 11 so as to control the temperature of the polymeric spinning solution supplied to and introduced into the tubular body 40 .

Due to the above temperature control device, the temperature of the electrospinning can be performed at a high temperature (50 to 100 ° C) as compared with a normal temperature. Conventional electrospinning is carried out at room temperature, but there is a problem in that the solute of the polymer solution is insoluble in the solvent at room temperature. Therefore, MEK (methyl ether ketone), THF (tetrahydrofuran), and alcohol diluent are used to easily prepare the polymer solution.

However, in the method using the diluent described above, the concentration of the solute is lowered to lower the efficiency of electrospinning, and problems such as environmental contamination due to the generation of an excessive residual solvent and an increase in the unit cost of production have been caused. In order to solve the problem of electrospinning at room temperature, a temperature regulating device 60 in the form of a heat ray 41 is formed in a spiral shape around the inner periphery of the tubular body 40 of the nozzle block 11, And the temperature of the polymer solution was controlled.

6 is a perspective view schematically showing a nozzle block installed in a low melting point polymer unit of an electrospinning apparatus according to the present invention. The nozzle arranged in the low melting point polymer unit may be applied to the front face portion of the substrate, but is preferably applied to a specific portion of the substrate if necessary. In Fig. 6, the nozzles are divided into five groups of nine nozzles, one at the center and two at the bottom in the upper part. However, the arrangement of the nozzle and the nozzle block is not limited thereto, and it is obvious that those skilled in the art can appropriately design, change and arrange the nozzle in consideration of the number of the nozzles and the amount of the low melting point polymer to be radiated.

FIGS. 7 to 10 are plan views schematically showing an operation process of electrospinning a polymer spinning solution on the same plane of a substrate through nozzles of each nozzle tube of an electrospinning device for manufacturing a nanofiber web according to the present invention. The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i having a plurality of nozzles 111a linearly arranged on the upper surface thereof are connected to the substrate 115 on the nozzle block 111, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i are connected to the spinning liquid main tank 8, The polymer spinning solution filled in the tank 8 is supplied.

The nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are connected to the spinning liquid main tank 8 through a supply pipe 240, A plurality of nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i and a spinning liquid main tank 8 are branched.

At this time, the supply piping 240, which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i in the spinning liquid main tank 8, And the supply amount adjusting means comprises valves 212, 213, 214, and 233.

The valves 212, 213, 214 and 233 are connected to the supply pipe 240 which is communicated to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i in the spinning liquid main tank 8, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 by the respective valves 212, 213, 214, 233, Is controlled by an on-off system in which the supply of the polymer solution is controlled and controlled.

That is, when the polymer spinning solution is supplied to the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 through the supply pipe 240, The valves 212, 213, 214 and 233 provided in the supply pipe 240 for supplying the main tank 8 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, The nozzle tubes 112b, 112d, 112f, 112g, 112g, 112d, 112d, 112d, 112e, 112f, 112g, 112h, 112i are arranged in the nozzle block 111, 112b, 112c, and 112d in the spinning liquid main tank 8 by opening and closing the valves 212, 213, 214, and 233 such that the polymer solution is selectively supplied only to the nozzles 112a, 112b, , 112e, 112f, 112g, 112h, and 112i of the polymeric spinning solution is controlled and controlled.

The spray liquid main tank 8 and the nozzle tubes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, and 112i are connected to the supply pipe 240 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i in the spinning liquid main tank 8 are provided with valves 212, 213, 214, The nozzle tubes 112a, 112b, 112c, 112d, and 112d, which are arranged in the nozzle block 111 by opening specific valves 212, 213, 214, and 233 among the plurality of valves 212, 213, 214, 112b, 112d, 112f, 112g, 112h, 112i of the nozzle tubes 112a, 112b, 112e, 112f, 112g, 112h, 112i, 213, 214, and 233, such as blocking the supply of the polymer solution, to only the nozzle tubes 112a, 112c, and 112e at specific positions in the nozzle tube body arranged in the nozzle block 111, Room used by In the main tank 8 is supplied to the polymer spinning solution to be supplied to each nozzle tube (112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i) is adjusted and controlled.

That is, the nozzles 111a provided in the supply pipe 240 and the nozzle pipes 112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h and 112i are addressed, (111a).

The means for regulating the amount of radiation comprises valves 212, 213, 214 and 233.

By providing the valves 212, 213, 214 and 233 as the radiation amount adjusting means, it is possible to supply the respective nozzles 111a from the supply pipe 240 by opening and closing the valves 212, 213, 214 and 233 The valves 212, 213, 214 and 233 are controllably connected to a controller (not shown), and the valves 212, 213, 214, It is also possible that the opening and closing of the valves 212, 213, 214, and 233 are manually controlled according to the situation of the field and the operator.

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 also referred to as machine direction / longitudinal direction, and CD is referred to as 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 (g / m 2). In recent years, for the purpose of making the air filter and the unit lighter and more compact, a type of the filter having a smaller depth is required, and if the filter material having the same filtration area is put in the unit, the filter material faces contact each other due to the thickness of the filter material, There has been a problem in that the pressure loss of the air filter unit remarkably increases. To solve this problem, there has been an attempt to reduce the thickness of the filter material for the air filter, that is, to reduce the basis weight. However, such an attempt has been made to reduce the basis weight of the filter, and it is possible to solve the pressure loss of the air filter unit sufficiently when the basis weight is reduced for a specific portion of the filter for each specific industrial field to which the filter is applied. The strength of the filter medium can be maintained.

FIGS. 11 and 12 are plan views schematically showing an operation process of sequentially injecting the low-melting-point polymer and the polymer spinning solution through the arrangement of the nozzle blocks in the low melting point polymer unit as shown in FIG. 6, wherein the arrangement of the nozzle blocks as shown in FIG. The low melting point polymer is applied to a portion of the substrate (one in the middle and two in the middle at the top) and then the polymer spinning solution is radiated to the front side of the substrate.

13 and Fig. 16 show a state in which the nozzle blocks provided in the low melting point polymer unit of the electrospinning apparatus according to the present invention are arranged in another form. Fig. 13 is arranged to face the longitudinal direction MD of the substrate, and Fig. 16 shows the shape arranged to face the width direction CD of the substrate. The operation of sequentially spraying the low-melting-point polymer and the polymer solution according to the spray of the nozzle as shown in FIGS. 13 and 16 is shown in FIGS. 14 and 15 and FIGS. 17 and 18, respectively.

In the present invention, a substrate selected from cellulose, a binary system and a poly (terephthalate) is used as the long sheet 15, and a low melting point polyurethane, a low melting point polyester and a low melting point polyvinylidene fluoride are used as the low melting point polymer solution And polyvinylidene fluoride is used as the polymer for the spinning solution.

The cellulose base material used in the present invention is preferably composed of 100% cellulose, but cellulose having a total mass ratio of 70 to 90: 10 to 30 mass% of polyethylene terephthalate (PET) It is also possible to use a substrate having a cellulose base coated with a flame retardant coating.

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

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.

It is needless to say that the low melting point polyurethane, the low melting point polyester and the low melting point polyvinylidene fluoride may be used singly or in combination of two or more.

Hereinafter, a method of manufacturing the nanofiber filter of the present invention will be described using the electrospinning device.

(N, N-dimethylaceticamide) solvent to prepare a low-melting-point polymer solution, and the low melting point polyvinylidene fluoride, low melting point polyester, low melting point polyurethane, Is supplied to the main tank 8 connected to the polymer units 10a and 10c and the low melting point polymer solution supplied to the main tank 8 is supplied to the nozzle block 11 through the metering pump And is supplied continuously and quantitatively to the plurality of nozzles 12 of the nozzle. The low melting point polymer 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 form an adhesive layer having a basis weight of about 0.1 g / do.

Next, a polymer spinning solution in which polyvinylidene fluoride is dissolved in a solvent is supplied to a main tank 8 connected to spinning solution units 10b and 10d of the electrospinning apparatus.

In the present invention, the polyvinylidene fluoride nanofibers electrospun in the spinning solution units 10b and 10d are different in diameter. In order to change the diameters of electrospun nanofibers, it is necessary to control the intensity of the voltage, to adjust the gap between the nozzle and the collector, to control the concentration and viscosity of the spinning solution, or to control the moving speed of the long sheet . In order to vary the diameters of the nanofibers, the present invention controls the intensity of the voltage, but the scope of the present invention is not limited thereto.

Example 1

Melting polymeric unit 10a or 10c of the electrospinning apparatus was prepared by dissolving a low-polymerization polyurethane having a softening temperature of 80-100 ° C in a solvent of DMAc (N, N-dimethylaceticamide) In the main tank. A spinning solution in which polyvinylidene fluoride having a weight average molecular weight of 50,000 was dissolved in dimethylacetamide (N, N-dimethylacetamide, DMAc) was injected into a tank connected to spinning solution units 10b and 10d.

A distance between the electrode and the collector was 40 cm, an applied voltage of 20 kV, and an applied voltage of 70 캜 to form an adhesive layer having a basis weight of 0.1 g / m 2 on the base material in the low melting point polymer unit 10 a, And the distance between the collectors was 40 cm, and the applied voltage was 25 kV and 70 DEG C to form a polyvinylidene fluoride nanofiber layer having a basis weight of 0.5 g / m < 2 > and a diameter of 130 nm.

In the spinning solution unit 10d, polyvinylidene fluoride nanofiber layers having a basis weight of 0.5 g / m 2 and a diameter of 100 nm were formed by electrospinning at an applied voltage of 20 kV under the same electrospinning conditions.

Example 2

The same operation as in Example 1 was carried out except that the applied voltages at electrification in the spinning solution units 10b and 10d were changed to 17 kV and 25 kV, respectively. As a result, a polyvinylidene fluoride nanofiber layer having diameters of 150 nm and 100 nm, respectively, could be laminated.

Comparative Example 1

A cellulose substrate was used as a filter media.

Comparative Example 2

A polyvinylidene fluoride was electrospun on a cellulose substrate to form a laminate of polyvinylidene fluoride nanofiber nonwoven fabric to prepare a filter.

- Filtration efficiency measurement

The DOP test method was used to measure the efficiency of the fabricated nanofiber filter. The DOP test method measures the dioctyl phthalate (DOP) efficiency with an automated filter analyzer (AFT) of TSI 3160 from TSI Incorporated and measures the permeability, filter efficiency and differential pressure of the filter media material .

The automation analyzer is a device that automatically measures the velocity of air, DOP filtration efficiency, air permeability (permeability), etc. by passing DOP through the filter sheet by making particles of desired size and is a very important device for high efficiency filter.

The DOP% efficiency is defined as:

DOP% efficiency = (1 - (DOP concentration downstream / DOP concentration upstream)) 100

The filtration efficiencies of Examples 1 and 2 and Comparative Example 1 were measured by the above-mentioned methods and are shown in Table 1.

Example 1 Example 2 Comparative Example 1 0.35 탆 DOP
Filtration efficiency (%) 90 92 60

It can be seen that the filter including the nylon and polyvinylidene fluoride nanofiber layers manufactured through the embodiment of the present invention has a higher filtration efficiency than the filter of Comparative Example 1. [

- pressure drop and filter life measurement

The pressure drop of the fabricated nanofiber nonwoven filter was measured with ASHRAE 52.1 according to the flow rate of 50 / / m 3 , and the filter life was measured accordingly. Data comparing Example 1. 2 and Comparative Example 1 are shown in Table 2.

Example 1 Example 2 Comparative Example 1 Pressure drop (in.w.g) 4.2 4.0 7.8 Filter life
(month) 5.4 5.8 3.2

According to Table 2, it can be seen that the filter manufactured through the embodiment of the present invention has a lower pressure drop due to a lower pressure drop compared to the comparative example, and the filter has a longer life span, resulting in superior durability.

- whether or not the nano fiber nonwoven fabric is removed

As a result of measuring whether or not the fabricated nanofiber nonwoven fabric and the filter substrate were desorbed by the ASTM D 2724 method, the nanofiber nonwoven fabric was not desorbed in the filters manufactured in Examples 1 to 3, The filter had a tendency to desorb the nanofiber nonwoven fabric.

Accordingly, it can be seen that, in the nanofiber filter having the adhesive layer formed by electrospinning the low melting point polymer solution on the substrate as in the present invention, the separation between the substrate and the nanofiber layer and the nanofiber layer does not occur well.

- Viscosity adjustment result by temperature control device

[Example 6]

20% by weight of polyamic acid having a weight average molecular weight of 100,000 was dissolved in 80% by weight of a solvent of NN-dimethylacetamide (DMAc) to prepare a spinning solution having a concentration of 10% and a viscosity of 1000 cps and provided in the main tank 8 . Thereafter, the spinning solution was moved from the main tank 8 to the nozzle block, and then the distance between the nozzle block and the collector was 40 cm and the applied voltage was 25 kV. In the course of preparing the main storage tank, which is one of the storage tanks, the concentration of the spinning solution in the main tank was changed to 15%, and the viscosity was changed to 2000 cps. Thereafter, the temperature of the main tank was raised to 70 ° C to lower the viscosity to 1000 cps by the sensor of the temperature controller, and electrospun was obtained to obtain nanofibers.

[Example 7]

As the concentration of the spinning solution in the main tank 8 was changed to 20% by the overflowed solid content and the viscosity was increased, the temperature of the main tank 8 was adjusted to 65 ° C Was electrospinning in the same manner as in Example 6

[Example 8]

As the concentration of the spinning solution in the main tank 8 was changed to 25% by the overflowed solids, the temperature of the main storage tank was raised to 80 DEG C by a temperature controller to maintain the viscosity at 1000 cps as the viscosity increased. The electrospinning was carried out in the same manner as in Example 6.

[Example 9]

As the concentration of the spinning solution in the main tank 8 was changed to 30% by the overflowed solids, the temperature of the main storage tank was raised to 95 ° C by a temperature controller to maintain the viscosity at 1000 cps as the viscosity increased. The electrospinning was carried out in the same manner as in Example 6.

[Comparative Example 3]

20 wt% of polyamic acid having a weight average molecular weight of 100,000 was dissolved in 80 wt% of NN-dimethylacetamide (DMAc) solvent to prepare a spinning solution having a concentration of 10% and a viscosity of 1000 cps. Then, the spinning solution was moved from the main storage tank to the nozzle block, and then the distance between the nozzle block and the collector was 40 cm and the applied voltage was 25 kV. In the course of the subsequent spinning process, the overflowed solidified material was returned to the main storage tank, and the concentration of the spinning solution in the main storage tank was changed to 20%. To maintain the concentration again at 10%, DMAc was added And THF, which is a diluent, was added thereto to conduct electrospinning.

The viscosity of the nanofibers produced according to Examples 6 to 9 and Comparative Example 3 and the nanofiber yield

The spinning speed was measured at 0.2 g / m 2, and the results are shown in Table 3.

Example 6 Example 7 Example 8 Example 9 Comparative Example 3 density 15% 20% 25% 30% 10% Viscosity calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) calendar
(1,000 cps) Winding speed
(m / min) 20 25 30 35 10

According to Table 3, as the concentration of the embodiment is higher and the viscosity is constant as compared with the comparative example, as the amount of solid content to be stacked on the actual collector is increased during spinning, the winding speed is increased and the production amount is increased. Thus, it is expected that the embodiment will be able to obtain more efficient spinning and increased throughput than the comparative example.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Anyone with it will know easily.

1: electrospinning device, 3: feed roller,
5: take-up roller, 7: main control device,
8: main tank, 10a: low melting point polymer unit
10b: spinning liquid unit
11: nozzle block, 12: nozzle,
13: collector, 14, 14a, 14b: voltage generator,
15, 15a, 15b: long sheet, 16: auxiliary conveying device,
16a: auxiliary belt, 16b: auxiliary belt roller,
18: case, 19: insulating member,
30: Long sheet conveying speed adjusting device, 31: Buffer section,
33, 33 ': support roller, 35: regulating roller,
40: tube body, 41, 42: heat wire,
43: pipe, 60: thermostat
70: thickness measuring device, 80: air permeability measuring device,
90: laminating device, 111: nozzle block,
111a: nozzle 112: nozzle tube,
112a, 112b, 112c, 112d, 112e, 112f, 112g, 112h, 112i:
115: substrate, 115a, 115b, 115c: nanofiber web,
200: overflow device,
211, 231: stirring device, 212, 213, 214, 233: valve,
216: second transfer pipe, 218: second transfer control device,
220: intermediate tank, 222: second sensor,
230: regeneration tank, 232: first sensor,
240: supply piping, 242: supply control valve,
250: circulating fluid recovery path, 251: first transfer pipe,
300: VOC recycling apparatus, 310: condensing apparatus,
311, 321, 331, 332: piping, 320: distillation device,
330: solvent storage device, 404: air supply nozzle,
405: nozzle plate, 407: first spinning solution storage plate,
408: second spinning liquid storage plate, 410: overflow liquid temporary storage plate,
411: air storage plate, 412: overflow outlet,
413: air inlet,
414: nozzle support plate for supplying air, 415: overflow removing nozzle,
416: nozzle support plate for removing overflow, 500: multi-tubular nozzle,
501: inner tube, 502: outer tube,
503: the tip.

Claims (6)

A substrate;
A first nanofiber layer of polyvinylidene fluoride having a fiber diameter of 100 to 150 nm; And
A second polyvinylidene fluoride nanofiber layer having a fiber diameter of 80 to 150 nm;
Wherein the adhesion between the substrate and the first nanofiber layer, between the first nanofiber layer and the second nanofiber layer is bonded through an adhesive layer formed by electrospinning the low melting point polymer solution,
Wherein the first and second nanofiber layers are different in basis weight in the longitudinal direction or in the transverse direction. The method according to claim 1,
Wherein the low melting point polymer solution is selected from at least one selected from a low melting point polyester, a low melting point polyurethane, and a low melting point polyvinylidene fluoride. The method according to claim 1,
Wherein the low melting point polymer solution is electrospun on the entire surface or a part of the substrate and the first nanofiber layer. 4. The method according to any one of claims 1 to 3,
Wherein the first and second nanofiber layers are formed by electrospinning a polyvinylidene fluoride solution at a temperature of 50 to 100 ° C. delete The method according to claim 1,
Wherein the polyvinylidene fluoride solution for forming the first and second nanofiber layers is maintained at a viscosity of 1,000 cps to 3,000 cps through a temperature controller.
KR1020150057474A 2015-04-23 2015-04-23 Filter including polyvinylidene fluoride nanofiber having multiple fiber-diameter group with low melting point polymer adhension layer and its manufacturing method KR101778250B1 (en)

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KR101292657B1 (en) * 2013-02-06 2013-08-23 톱텍에이치앤에스 주식회사 A hybrid non-woven separator having the inverted structure
KR101479756B1 (en) 2013-08-01 2015-01-06 (주)에프티이앤이 Multi-layered nanofiber filter with excellent heat-resisting property and its method

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KR101292657B1 (en) * 2013-02-06 2013-08-23 톱텍에이치앤에스 주식회사 A hybrid non-woven separator having the inverted structure
KR101479756B1 (en) 2013-08-01 2015-01-06 (주)에프티이앤이 Multi-layered nanofiber filter with excellent heat-resisting property and its method

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