KR20170071870A - Antimicrobial nano mask containing metal plating nanofiber and method for producing same - Google Patents

Antimicrobial nano mask containing metal plating nanofiber and method for producing same Download PDF

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KR20170071870A
KR20170071870A KR1020150180041A KR20150180041A KR20170071870A KR 20170071870 A KR20170071870 A KR 20170071870A KR 1020150180041 A KR1020150180041 A KR 1020150180041A KR 20150180041 A KR20150180041 A KR 20150180041A KR 20170071870 A KR20170071870 A KR 20170071870A
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impeller
metal
solution
curing agent
melting point
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KR1020150180041A
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Korean (ko)
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KR101753055B1 (en
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박종철
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(주)에프티이앤이
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D06M11/42—Oxides or hydroxides of copper, silver or gold
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B18/00—Breathing masks or helmets, e.g. affording protection against chemical agents or for use at high altitudes or incorporating a pump or compressor for reducing the inhalation effort
    • A62B18/02—Masks
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B18/00—Breathing masks or helmets, e.g. affording protection against chemical agents or for use at high altitudes or incorporating a pump or compressor for reducing the inhalation effort
    • A62B18/02—Masks
    • A62B18/025—Halfmasks
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B23/00—Filters for breathing-protection purposes
    • A62B23/02—Filters for breathing-protection purposes for respirators
    • A62B23/025—Filters for breathing-protection purposes for respirators the filter having substantially the shape of a mask
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • 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
    • D04H1/40—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
    • D04H1/58—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 by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—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 by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Management (AREA)
  • General Health & Medical Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pulmonology (AREA)
  • Mechanical Engineering (AREA)
  • Zoology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The present invention relates to an antimicrobial nanomask including metal-plated nanofibers using a metal plating apparatus and a method of manufacturing the same. More particularly, the present invention relates to a nanofiber web produced by electrospinning, The present invention relates to an antimicrobial nanomask including a metal-plated nanofiber applicable to a nanomask, and a method of manufacturing the same.

Description

TECHNICAL FIELD The present invention relates to an antimicrobial nano-mask including metal-coated nanofibers,

The present invention relates to an antimicrobial nanomask including metal-plated nanofibers using a metal plating apparatus and a method of manufacturing the same. More particularly, the present invention relates to a nanofiber web produced by electrospinning, The present invention relates to an antimicrobial nanomask including a metal-plated nanofiber applicable to a nanomask, and a method of manufacturing the same.

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, with the spread of environmentally harmful viruses, bacteria, and bacteria and fungi that threaten human health, efforts to effectively block the viruses and bacteria are continuing.

 Conventionally, organic antibacterial agents have been conventionally used to combine antibacterial functions with plastic products such as plastics, which are frequently used in daily life. However, organic antibacterial agents have a tendency to refrain from use due to increase in tolerance and harmfulness to the human body due to their basic characteristics.

In order to replace these organic antimicrobial agents, the emergence of inorganic antibacterial agents and the emergence of nanotechnology are leading to the possibility of implementing new technologies.

In recent years, along with the development of the textile industry, technologies for nanofibers produced by electrospinning have been developed.

In this way, nanofibers produced by electrospinning are very simple in structure compared to equipment and apparatus for the production of other textile products, and can be electrospun to polymeric materials, which can add various structures and versatility There are various studies to utilize this.

Here, a nanofiber refers to a microfiber having a diameter of only a few tens to several hundreds of nanometers, and is produced by an electric field generated by electrospinning. 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 addition, the nanofibers produced by electrospinning have a very large surface area in terms of volume and a fineness of tens to hundreds of nanometers.

On the other hand, nanofibers produced by electrospinning can be used for various purposes such as polyacrylonitrile (PAN), polyethylene oxide (PEO), polyethylene terephthalate (PET), polyurethane (PU), polyvinyl Polymers such as polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), biodegradable polymer (PLGA), PGA, polyacrylamide (PAA), cellulose, gelatin and chitosan It is possible to apply most of the polymer materials such as the material.

The nanofibers obtained by electrospinning under high voltage conditions using a polymeric material as described above are susceptible to damage caused by sensor electrodes such as an ECG sensor and a piezoelectric sensor, Shielding films for electromagnetic shielding and antibacterial masks, and the like.

On the other hand, electroless metal plating is a technique for performing metal plating on a non-conducting material or a complicated-shaped part, and can be plated at a lower cost than metal plating by sputtering deposition through an expensive vacuum apparatus, (Cu), nickel (Ni), gold (Ag), silver (Au) or the like.

In addition, the use of electroless metal plating on a textile fabric has been commercialized and widely applied. Electroless metal plating is performed on a polyethylene terephthalate (PET) fabric and a nonwoven fabric with a conductive metal such as nickel (Ni) Shielding film for electromagnetic wave shielding.

Here, when a nanofiber web is produced by electrospinning with a high-strength steel raw material such as polyethylene terephthalate (PET) or polyacrylonitrile (PAN), and metal plating is performed, A metal plating is performed by a general roll-bath dip-type plating apparatus including a bath filled with an amount of water and a plurality of rollers arranged in a pair of upper and lower pairs in the bath, , The nanofiber web passes between the pair of rollers to perform cleaning and metal plating operations.

Here, it is difficult to realize metal plating on all kinds of nanofibers due to variables such as the characteristics of raw materials, types of organic solvents, and molar ratio during metal plating of the nanofiber web through a roll-bath submerged plating apparatus There is a problem in that metal plating can be performed only on a nanofiber web having a tensile strength of 1 kgf or more.

That is, since the nanofiber web prepared by general electrospinning does not have sufficient tensile strength for metal plating, it is possible to perform metal plating only on nanofiber webs of 1 kgf or more in metal plating.

In the roll-bath submerged plating apparatus, a general-sized nanofiber web can be plated with metal, but nanofibers used for specific purposes and purposes, namely, those having a tensile strength of less than 1 kgf or a thickness of less than 10 μm The object of the present invention is to provide a thin film nanofiber having high functional properties.

Further, since the nanofiber web for performing the metal plating has a length of at least 100 m or more, there is a problem that a lot of cost and energy are consumed.

In addition, there is a problem in that the quality of the metal-plated nanofiber web deteriorates during metal plating and the metal plating of the nanofiber web is uneven.

Accordingly, there is a need for a new plating apparatus for performing metal plating on special purpose high-functional thin film nanofibers.

On the other hand, nanofiber webs produced by electrospinning are applied as electrodes of precision sensors such as ECG sensors (electrochemical sensors) due to the developed pores between the fibers. However, when used in special applications such as precision sensors, In order to emphasize the pore function, metal plating should be performed after omitting the calendering process of applying high temperature and high pressure to the nanofiber web. In this case, electroless plating is impossible due to tensile strength and deterioration of bonding force between fibers There was a problem.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a nanofiber web in which a nanofiber web is inserted, And an antibacterial nano-mask including the metal-coated nano-fiber and a method for producing the same. The present invention also provides a method for producing the same.

According to an aspect of the present invention, there is provided a method of manufacturing a nanofiber, comprising: preparing a nanofiber by electrospunning a polymer spinning solution; Inserting the nanofibers into a stacked impeller, and then mounting a stacked impeller in a bath; Dissolving the chemical plating solution and distilled water in the bath, adding sodium hydroxide (NaOH), and stirring the laminated impeller at a low speed; Coating a bass lid on the body of the bass, adding a glucose reducing agent thereto, stirring the mixture, and performing metal plating to produce metal-coated nanofibers; Depositing the metal-plated nanofibers on a first substrate; And laminating a second substrate on the metal plated nanofibers; The present invention also provides a method for producing an antibacterial nano-mask.

Here, the chemical plating solution may include silver (Ag) or gold (Au), and the adhesion between the metal-plated nanofibers and the first and second substrates may be performed using a low-melting-point polymer solution or an epoxy resin- Wherein the adhesive layer is adhered through an adhesive layer formed by electrospinning a curing agent solution.

The low melting point polymer solution or the epoxy resin-curing agent solution is electrospun on the entire surface or a part of the substrate and the metal plated nanofiber, and the low melting point polymer solution is a low melting point polyester, Polyurethane, and low melting point polyvinylidene fluoride. The curing agent is one selected from the group consisting of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent. A method of manufacturing a nanomask is provided.

INDUSTRIAL APPLICABILITY As described above, the present invention having the above-described structure can produce nanofiber webs that are functionally excellent by performing metal plating of nanofiber webs in which the physical properties are insufficient and degraded.

In addition, the antibacterial nanomask including the metal-plated nanofibers using the metal plating method of the present invention has an effect of exhibiting excellent antibacterial activity and can reduce the metal precipitate generated when the metal plating is performed with a chemical plating amount, In addition to being capable of metal plating on a nanofiber web, it is possible to manufacture various kinds of products required by metal plating on all types of fiber structure using nanofibers, and the metal plating process and efficiency can be visually inspected It is possible to improve the manufacturing processability and reduce the product cost, and the convenience of the operation of the metal plating apparatus and the reliability of the metal-plated nanofiber web can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front view schematically showing a metal plating apparatus of a nanofiber web according to the present invention,
FIG. 2 is a side view schematically showing a metal plating apparatus of a nanofiber web according to the present invention in a closed state;
3 is a schematic view of an impeller case of a metal plating apparatus for a nanofiber web according to the present invention,
4 is a schematic view of an impeller member according to an embodiment of a metal plating apparatus for a nanofiber web according to the present invention,
5 is a schematic view of a stacked impeller in which an impeller member is inserted into an impeller case of a metal plating apparatus for a nanofiber web according to the present invention,
6 is a schematic view of an impeller member according to another embodiment of a metal plating apparatus for a nanofiber web according to the present invention,
FIG. 7 is a schematic view of an impeller member according to another embodiment of a metal plating apparatus for a nanofiber web according to the present invention,
8 is a schematic view of an electrospinning apparatus for producing a nanofiber web according to the present invention,
9 to 10 are views schematically showing a process in which an impeller member is inserted into an impeller case of a laminated impeller of a metal plating apparatus for a nanofiber web according to the present invention,
11 is a view showing a metal-plated nanofiber web through a metal plating apparatus according to the present invention,
12 is a view of a metal plated nanofiber web through a conventional metal plating apparatus,
13 is a side view schematically showing an electrospinning apparatus according to the present invention,
14 is a perspective view schematically showing a nozzle block installed in a low melting point polymer unit or an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention,
FIGS. 15 and 16 are plan views schematically showing an operation process in which a low melting point polymer and a polymer spinning solution are sequentially injected through arrangement of a nozzle block in a low melting point polymer unit or an epoxy resin-curing agent unit as shown in FIG. 14;
17 is a perspective view schematically showing still another form of a nozzle block installed in a low melting point polymer unit or an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention,
FIGS. 18 and 19 are plan views schematically showing an operation sequence in which the low melting point polymer and the polymer spinning solution are sequentially injected through the arrangement of the nozzle blocks in the low melting point polymer unit or the epoxy resin-
20 is a perspective view schematically showing still another form of a nozzle block installed in a low melting point polymer unit or an epoxy resin-curing agent unit of an electrospinning apparatus according to the present invention,
FIGS. 21 and 22 are plan views schematically showing an operation of sequentially injecting a low-melting-point polymer solution or an epoxy resin-curing agent solution through arrangement of a nozzle block in a low melting point polymer unit or an epoxy resin-curing agent unit as shown in FIG.

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.

FIG. 1 is a front view schematically showing an open state of a metal plating apparatus of a nanofiber web according to the present invention, FIG. 2 is a side view schematically showing a closed state of a metal plating apparatus of a nanofiber web according to the present invention, FIG. 3 is a schematic view of an impeller case of a metal plating apparatus for a nanofiber web according to the present invention, and FIG. 4 is a schematic view of an impeller member according to an embodiment of the apparatus for metal plating of a nanofiber web according to the present invention. And FIG. 5 is a schematic view of a stacked impeller in which an impeller member is inserted into an impeller case of a metal plating apparatus for a nanofiber web according to the present invention. FIG. 6 is a cross- FIG. 7 is a schematic view of an impeller member according to another embodiment of the present invention. FIG. 7 is a cross- FIG. 8 is a schematic view of an electrospinning apparatus for producing a nanofiber web according to the present invention, and FIGS. 9 to 10 are schematic views of an impeller member according to another embodiment of the present invention FIG. 11 is a view illustrating a process of inserting an impeller member into an impeller case of a laminated impeller of a metal plating apparatus of a nanofiber web, FIG. 11 is a view showing a metal-plated nanofiber web through a metal plating apparatus according to the present invention And Fig. 12 is a view showing a metal-plated nanofiber web through a general metal plating apparatus.

As shown in the figure, a metal plating apparatus 1 for a nanofiber web according to the present invention comprises a bath 10, a stacked impeller 30, and a controller 50.

The bath 10 includes a bath body 11 filled with a chemical plating solution made of an antibacterial or conductive metal such as Au, Ag, Cu or Ni, And a bath lid 15 which is vertically movable upward and downward from the upper portion of the bath main body 11 so as to be opened and closed.

At this time, it is preferable that the bath 10 is made of a glass material so that an operator can visually confirm the metal plating process when metal plating is performed on the nanofiber web 3, but the present invention is not limited thereto.

Here, a discharge unit 12 for discharging chemical plating solution to be filled in the body 11 is formed in the lower part of the bath body 11. That is, a discharge unit 12 for discharging the waste solution generated after the metal plating process is formed in the lower part of the bath body 11, and the discharge unit 12 is made of a Teflon material resistant to strong acid solution and strong alkali solution But is not limited thereto.

A driving motor 17 is provided at the center of the outer surface of the basal lid 15 and one end of the shaft 18 is rotatably connected to the driving motor 17, The end portion is inserted into the body of the bath body 11 through the bath lid 15 at a predetermined portion.

At this time, the bath lid 15 is moved upward or downward by a predetermined distance or more to facilitate mounting and mounting of the stacked impeller 30 in the bath body 11.

The impeller 30 has a nanofiber web 3 interposed therebetween. The impeller 30 is rotatably installed in the bath 10 and is stirred by the chemical plating solution filled in the bath 10, (3) is metal-plated, and comprises an impeller case (31) and an impeller member (37).

The impeller case 31 is formed of a frame-shaped body having a rectangular parallelepiped shape. The impeller case 31 has a pair of spaced apart spaced apart impeller cases 31a and 31b. So as to be in contact with the pair of impeller cases 31a and 31b.

A connecting portion 32a is formed at an upper end of the connecting rod 32 to be connected to a shaft end portion of the driving motor 17 by a fastening member such as a bolt or the like. And a scrubber 32 for circulating the chemical solution filled in the chemical solution tank.

The connecting rod 32 is provided with a scrubber 32b and the scrubber 32b is simultaneously rotated by the rotation of the stacked impeller 30 driven by the driving motor 17 to rotate the bath 10, The amount of the metal precipitate in the solution decreases as much as possible.

Here, the scrubber 32b is formed as a semicircular plate-shaped body, and is provided at a lower side of the connecting rod 32 as a pair of spaced apart from each other.

In an embodiment of the present invention, the scrubber 32b is provided at a lower end of the connecting rod 32 at a predetermined interval, but the number of the scrubber 32b is not limited thereto.

In addition, although the scrubber 32b is formed as a semicircular plate-shaped body in the embodiment of the present invention, the scrubber 32b may be formed as a triangular plate-shaped body or a rectangular plate-like body, The shape and size of the scrubber 32b can be variously changed.

An installation space 33 for installing the impeller member 37 is formed in the impeller case 31. An installation hole 34a for inserting the impeller member 37 is formed on one side of the installation space 33, And a stopper 34b is formed at each edge of the other side surface.

The impeller member 37 slidably inserted into the installation space 33 through the installation hole 34a formed at one side of the impeller case 31 formed in the frame shape body is prevented from being detached to the other side.

The impeller member 37 is inserted into the installation space 33 of the impeller case 31 through the installation hole 34a only when the impeller member 37 is inserted into the installation space 33 of the impeller case 31. [ The member 37 can be moved in and out.

At least one or more than one pinhole 34 for inserting a fixing pin (not shown) is formed at one edge of the impeller case 31 at the front and rear sides thereof.

That is, the impeller member 37 inserted into the installation space 33 when the impeller member 37 is inserted into the installation space 33 through the installation hole 34a formed on one side surface of the impeller case 31 A pinhole 34 for inserting a fixing pin is formed at the front and rear edges of one side of the impeller case 31 in which the installation hole 34a is formed.

After the impeller member 37 is inserted into the installation space 33 through the installation hole 34a of the impeller case 31 and the fixing pin is inserted into the pin hole 34, The impeller member 37 is prevented from being detached by the fixing pin and is easily fixed to the installation space 33. [

Meanwhile, the pair of impeller cases 31a and 31b are positioned opposite to each other with the connecting rod 32 as a center. That is, the pair of impeller cases 31a and 31b are positioned such that the connecting rods 32 are interposed therebetween, and one of the impeller cases 31a is positioned so as to form an installation hole 34a in one direction, The other impeller case 31b is positioned such that an installation hole 34a is formed in the other direction, and the pair of impeller cases 31a and 31b are opposed to each other such that the installation holes 34a are positioned in mutually opposite directions .

The mounting holes 34a of the pair of impeller cases 31a and 31b are positioned opposite to each other with respect to the connecting rod 32 so that the mounting holes 34a of the pair of impeller cases 31a and 31b are positioned in opposite directions, The mounting holes 34a of the cases 31a and 31b may be positioned so as to face the same direction, but the present invention is not limited thereto.

The impeller member 37 is formed of a rectangular parallelepiped. The impeller member 37 is stacked on at least two or more of the mounting spaces 33 of the impeller case 31.

The impeller member 37 and the nano fiber web 3 are inserted into the installation space 33 of the impeller case 31 so that the impeller member 37 and the nano- And is formed to correspond to the size and shape of the installation space 33.

As described above, the impeller member 37, which is formed by stacking a plurality of the nano-fiber webs 3 interposed between the impeller members 37, is inserted into the installation space 33 of the impeller case 31 And the metal plating is performed on the nanofiber web 3 by immersing and watering the chemical plating solution filled in the bath 10.

To this end, the impeller member 37 is provided with an inflow hole 38 for introducing the chemical plating solution filled in the bath 10 into the nanofiber web 3 interposed between the impeller members 37 to be plated with metal And the inflow hole 38 is divided into at least two or more.

The inflow hole 38 is divided into the impeller member 37 so as to be penetrated so that the nanofiber web 3 interposed between the impeller members 37 is exposed to the outside, And the metal plating is facilitated by flowing into the nanofiber web 3 through the respective inflow holes 38 where the chemical plating solution is divided into the impeller member 37 at the time of metal plating.

In addition, when the stacked impeller 30 having the nanofiber web 3 interposed thereon is rotated in the bath 10 for the metal plating, the pressure applied to the nanofiber web 3 is reduced so that the stacked impeller 30 can be stably .

In the embodiment of the present invention, the impeller member 37 is formed with 28 inlet holes 38, but if it is interposed between the impeller members 37 and is easy to be metal plated through the chemical plating solution, As shown in the drawing, the impeller member 37 'may be divided into four inflow holes 38' to perform metal plating on the nanofiber web 3, and as shown in FIG. 7, , The impeller member 37 "may be divided into six inflow holes 38" to perform metal plating on the nanofiber web 3, but the present invention is not limited thereto.

At least one or more pinholes 39 for inserting fixing pins (not shown) of the impeller case 31 are formed at one edge of the front and rear surfaces of the impeller member 37. That is, after the impeller member 37 is inserted into the impeller case 31, a pinhole 39 for inserting the fixing pin to prevent the detachment of the impeller member 37 is formed.

The pinhole 39 penetrating the impeller member 37 is formed at the same position as the pinhole 34 formed through the impeller case 31 and is inserted into the pinhole 39 Is formed to have the same size and diameter as the pinhole 34 formed through the impeller case 31.

After the impeller member 37 is inserted into the impeller case 31, the fixing pin is inserted into the pin hole 39 formed through the impeller member 37 and the pin hole 34 formed through the impeller case 31 The impeller member 37 inserted into the impeller case 31 is prevented from being separated from the impeller member 37 and is easily fixed.

The impeller member 37 is inserted into the impeller case 31 and formed on the front and back surfaces of the impeller cases 31a and 31b exposed to the inflow hole 38 of the impeller member 37 as a plate- A plurality of pinholes (not shown) are formed at the edges of the guide so that the impeller member 37 is mounted on the front and rear surfaces of the impeller cases 31a and 31b, However, the present invention is not limited to this.

The controller 50 is controllably connected to the bath 10 and the stacked impeller 30. That is, the control unit 50 includes a bath cover 15 that is opened and closed on the bath main body 11, and a discharge unit 12 that is filled with the metal plating-completed chemical solution in the bath main body 11 Controls the driving motor 17 to rotate the stacked bath 10 functioning and immersed in the chemical plating solution in the bath 10.

Here, it is preferable that the controller 50 is provided inside the operation panel capable of operation for metal plating by the operator, but the present invention is not limited thereto.

The bath 10 is provided with a cooling / heating circulator (not shown) for controlling the temperature of the bath 10 while circulating the silicone oil to the outside of the bath 10, (10) to a constant temperature.

For this purpose, it is preferable that a separate jacket, tube or pie for circulating the silicone oil is provided on the outer side of the bath 10, but it is not limited thereto.

Meanwhile, the cooling / heating circulator is preferably configured to control the temperature in the bath 10 within a range of -20 ° C to 200 ° C, but is not limited thereto.

As described above, the temperature of the chemical plating solution filled in the bath 10 by the cooling / heating circulator is adjusted to a constant temperature, whereby the temperature of the nanofiber web 3 interposed in the stacked impeller 30 in the bath 1 The metal plating efficiency can be improved.

The cooling / heating circulator can be integrally provided in the bath 10 of the metal plating apparatus 1 of the nanofiber web according to the present invention, and can be connected to one side of the bath 10 It is possible.

Hereinafter, the operation of the metal plating apparatus for a nanofiber web according to the present invention will be described with reference to FIGS. 8 to 12. FIG.

First, the nanofiber web 3 is produced through electrospinning. At this time, as a raw material of the polymer spinning solution for producing the nanofiber web 3, a solution of the above-mentioned polymer which is a synthetic resin material capable of electrospinning in a suitable solvent is used, and the type of the solvent is not limited as long as it can dissolve the polymer But not limited to, polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride, nylon, polyvinyl acetate, polymethylmethacrylate, polyacrylonitrile (PAN), polyurethane (PUR) (PBA), polyvinyl butyral, polyvinyl chloride, polyethylene imine, polyolefin, polylactic acid (PLA), polyvinyl acetate (PVAc), polyethylene naphthalate (PEN) There are polyvinyl alcohol (PVA), polyethylene imide (PEI), polycaprolactone (PCL), polylactic acid glyceric acid (PLGA), silk, cellulose, chitosan, The present invention relates to a method for manufacturing a semiconductor device, which comprises the steps of: forming a base material and a heat resistant polymer material such as polyamide, polyimide, polyamideimide, poly (meta-phenylene isophthalamide), polysulfone, polyetherketone, polyetherimide, polyethylene terephthalate, Aromatic polyesters such as polyethylene naphthalate, polyphosphazenes such as polytetrafluoroethylene, polydiphenoxaphospazene and polybis [2- (2-methoxyethoxy) phosphazene], polyurethanes and polyethers Polyurethane copolymer containing urethane, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and the like are preferably used in a commercial manner.

In addition, the spinning solution is a solution prepared by dissolving the above-mentioned polymer which is a synthetic resin material capable of electrospinning in a suitable solvent, and the type of solvent is not limited as long as it can dissolve the polymer. For example, phenol, formic acid, sulfuric acid, m - Cresol, thifluoroacetone and hydride / dichloromethane, water, N-methylmorpholine N-oxide, chloroform, tetrahydrofuran and aliphatic ketone groups such as methyl isobutyl ketone, methyl ethyl ketone, aliphatic hydroxyl group hexane, tetrachlorethylene, acetone, propylene glycol, diethylene glycol, ethylene glycol as a glycol group, trichlorethylene as a halogen compound group, ethylene glycol, ethylene glycol, , Dichloromethane, aromatic compounds such as toluene, xylene, aliphatic cyclic compound groups such as cyclohexanone, cyclohexane And esters such as n-butyl acetate, ethyl acetate, butyl cellosolve as an aliphatic ether group, acetic acid 2-ethoxy ethanol, 2-ethoxy ethanol, dimethyl formamide and dimethylacetamide, Type solvent may be mixed and used. The spinning solution preferably contains an additive such as a conductivity improver.

As shown in Fig. 8, the polymer spinning solution thus prepared is filled in a spinning liquid main tank (not shown) of the electrospinning device 100, and then the nanofiber web 3 is produced by electrospinning.

At this time, the electrospinning device 100 includes a spinning liquid main tank (not shown) in which a polymer spinning solution is filled, a metering pump (not shown) for supplying a polymer spinning solution filled in the spinning solution main tank in a quantitative manner, A nozzle block 111 for discharging the spinning liquid in the spinning liquid main tank and having a plurality of nozzles 112 arranged in a pin shape and a polymer spinning solution injected from the nozzle 112 of the nozzle block 111, A collector 113 installed at a predetermined distance from the nozzle 112 and a unit 110 or 110 'accommodating therein a voltage generator 114 for generating a voltage in the collector 113 And at least one of the units 110 and 110 'is continuously arranged in the horizontal direction.

The electrospinning apparatus 100 according to the present invention is configured such that the polymer spinning solution filled in the spinning liquid main tank provided in each unit 110, 110 'is supplied to a plurality of nozzles And the polymer spinning solution supplied to the nozzle 112 is radiated and focused on the collector 113 with a high voltage applied thereto through the nozzle 112, And is then radiated and focused onto the nanofibers 115 to form a nanofiber web.

The polymer spinning liquid filled in the spinning liquid main tank in any one of the plurality of units 110 and 110 'of the electrospinning apparatus 100 is discharged through the nozzle 112 to the release surface of the collector 113, (Not shown) provided on both sides of the collector 113, and the polymer spinning solution injected onto the release paper 115 is accumulated on the release paper 115, The releasing paper 115 is conveyed by driving the belt (not shown) by rotation, and is placed in the other unit 110 ', and is manufactured as a final product while repeating the above-described process.

The nanofiber web 3 prepared as described above is installed in the metal plating apparatus 1 of the nanofiber web according to the present invention.

That is, after separating the nanofiber web 3 electrospun on the release paper sheet, the separated nanofiber web 3 is laminated on the laminate impeller 30, and the laminate impeller having the nanofiber web 3 stacked thereon 30) is installed in the bath (10).

In other words, after separating the nanofiber web 3 on the release paper, the separated nanofiber web 3 is repeatedly interposed between the impeller members 37 of the stacked impeller 30, and the nanofiber web 3 The impeller member 37 having a plurality of laminated layers is inserted through an installation hole 34a formed in the pair of impeller cases 31a and 31b and the impeller member 37 Is inserted into the installation space 33 through the installation holes 34a of the impeller cases 31a and 31b and inserted into the installation space 33 of the impeller cases 31a and 31b The impeller member 37 having the plurality of laminated layers formed thereon is brought into contact with the stopper 34b so as to be placed on the installation space 33 and then fixed to the pinholes 34 of the impeller cases 31a and 31b, (Not shown) and a pin (not shown) is attached to the pin hole 39 of the impeller member 37, And an impeller member 37 laminated on the installation space 33 of each of the impeller cases 31a and 31b is fixed and a connecting rod 32 interposed between the pair of impeller cases 31a and 31b Is fastened to the shaft 18 connected to the driving motor 17 of the vessel lid 15 by the fastening member to complete the mounting and mounting of the stacked impeller 30 in the vessel 10.

At this time, the bath body 11 of the bath 10 is filled with chemical plating solution made of antibacterial or conductive metal such as silver (Au), gold (Ag), copper (Cu) or nickel (Ni) The bass lid 15 is moved downward in the vertical direction to be coupled to the body 11 of the bass.

 As described above, the stacked impeller 30, which is mounted in the bath 10 by coupling the bath lid 15 to the bath body 11 while filling the chemical liquid in the bath 10, And is connected to the shaft of the drive motor 17 by the connecting rod 32 by driving the drive motor 17 provided in the bath cover 15 through the control unit 50, The nanofibrous web 3 laminated in the stacked impeller 30 is subjected to metal plating by rotating the impregnated layered impeller 30 with the function of the impregnated amount.

At this time, when the stacked impeller 30 rotates, the scrubber 32b provided at the lower end of the connecting rod 32 at the center between the pair of impeller cases 31a and 31b also rotates, and the rotation of the scrubber 32b The nanofibrous web 3 is circulated by circulating the chemical plating solution filled in the bath 10 and floating and floating the metal precipitation material having a large specific gravity included in the chemical plating solution deposited in the lower part of the bath 10, Thereby enhancing the metal plating efficiency.

The chemical plating solution filled in the bath 10 during rotation of the stacked impeller 30 is introduced into the impeller member 37 inserted into the impeller case 31 through the inflow holes 38 And the chemical plating solution introduced through each of the inflow holes 38 formed in the impeller member 37 is formed by metal plating each of the nanofiber webs 3 interposed between the impeller members 37.

The pressure applied to the nanofiber web 3 at the time of metal plating is applied to the nanofiber web 3 interposed between the impeller members 37 by the inflow hole 38 divided into the impeller members 37 Can be reduced and rotated in a stable manner.

The driving motor 17 is driven at a low speed to rotate the stacked impeller 30 so that the nano fiber web 3 in the stacked impeller 30 connected to the shaft of the driving motor 17 by the connecting rod 32 It prevents breakage and damage.

At this time, the temperature in the bath 10 is maintained at a constant temperature within a range of -20 ° C. to 200 ° C. by the cooling / heating circulator (not shown) to perform metal plating on the nanofiber web interposed in the stacked impeller 30 do.

As described above, when the nanofiber web 3 is metal-plated through the metal plating apparatus 1 of the nanofiber web according to the present invention, a stacked impeller (a plurality of nanofiber webs 3) 30 is rotated at a low speed to prevent entanglement, breakage and damage of the nanofiber web 3 and to circulate the silicone oil in the outer portion of the bath 10 with the cooling / heating circulator to adjust the temperature of the bath 10 By controlling the temperature to be constant, it is possible to manufacture a high-quality nano-fiber web 3 by keeping the temperature of the laminated impeller 30 functioning and flooding the chemical plating solution at a constant temperature.

Hereinafter, a method for producing an antibacterial nanomask using the metal-plated nanofibers produced by the above-described method will be described.

In the present invention, a substrate selected from cellulose, a binary system, and polyethylene terephthalate is used as a base material used for the production of the antibacterial nanomask. As the low melting point polymer solution, low melting point polyurethane, low melting point polyester and low melting point polyvinyl Lt; / RTI > fluoride is used.

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 two-component base material in the present invention is most preferably polyethylene terephthalate to which two components having different melting points are bonded. The polyethylene terephthalate two-component substrate may be classified into a sheath-core type, a side-by-side type, a C-type, and the like. In the case of the sheath-core type two-component substrate, the sheath portion is a low melting point polyethylene terephthalate, and the core portion is made of general polyethylene terephthalate. Wherein the sheath portion is about 10 to 90 wt%, and the core is about 90 to 10 wt%. The sheath portion acts as a thermal binder to form the outer surface of the binder fiber, has a melting point of about 80 to 150 占 폚, and the core has a melting point of about 160 to 250 占 폚. The CIS type heterogeneous base material used as an embodiment in the present invention includes an amorphous polyester copolymer in which a melting point is not exhibited by a conventional melting point analyzer in the sheath portion and preferably a relatively high melting point component Is a thermally adhesive composite fiber to be used.

The polyester copolymer contained in the sheath portion is a copolyester in which 50 to 70 mol% is a polyethylene terephthalate unit. As the copolymerizable acid component, isophthalic acid is preferably used in an amount of 30 to 50 mol%, but any other conventional dicarboxylic acid may be used.

As a high melting point component used as a core component, a polymer having a melting point of 160 ° C or higher is suitable. Examples of the high melting point component include polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene terephthalate copolymer and polypropylene.

The basis weight of the binary material is preferably 10 to 50 g / m 2 , and the basis weight of the polyethylene terephthalate material is preferably 50 to 300 g / m 2 .

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.

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]

Figure pat00001

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)

Figure pat00002

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)

Figure pat00003

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 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. Examples thereof include 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 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)

Figure pat00004

(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, Aliphatic sulfonic acids such as pentanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid and 1-dodecane sulfonic acid (for example, aliphatic sulfonic acids having 1 to 16 carbon atoms); Benzene sulfonic acid, 3- (linear or branched octadecyl) benzene sulfonic acid, 4- (straight or branched octyl) benzene sulfonic acid, 3- (linear or branched dodecyl 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.

The epoxy resin-curing agent may be an adhesive layer formed by electrospinning a mixed solvent obtained by mixing an epoxy resin and a curing agent. Alternatively, an adhesive layer may be formed by electrospinning the epoxy resin solution and the curing agent solution.

That is, the adhesive layer is formed by electrospinning an epoxy resin solution to form a first adhesive layer, and electrospinning a solution of a curing agent on the first adhesive layer to form a second adhesive layer.

On the other hand, the adhesive layer is formed by electrospinning an epoxy resin solution to form a first adhesive layer, electrospinning a solution of a curing agent on the first adhesive layer to form a second adhesive layer, and applying an epoxy resin solution onto the second adhesive layer by electrospinning And a third adhesive layer formed in the order of the first adhesive layer, the second adhesive layer, and the first adhesive layer.

The adhesive layer may be formed by electrospinning a solution of a curing agent to form a second adhesive layer, electrospinning an epoxy resin solution on the second adhesive layer to form a first adhesive layer, and applying a curing agent solution onto the first adhesive layer by electrospinning And a third adhesive layer formed in the order of the second adhesive layer, the first adhesive layer and the second adhesive layer by forming the second adhesive layer.

According to a preferred embodiment of the present invention, the low-melting-point polymer or the epoxy resin-curing agent is dissolved in a solvent, and the low-melting-point polymer or the epoxy resin-curing agent is dissolved in the main tank 8 connected to the low melting point polymer unit or the epoxy resin-curing agent unit 10a or 10b of the electrospinning apparatus And the low melting point polymer solution supplied to the main tank 8 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 low-melting-point polymer solution or the epoxy resin-curing agent solution supplied from each of the nozzles 12 is electrospun and converged on the first substrate located on the collector 13 with a high voltage applied thereto through the nozzle 12, To form an adhesive layer of 0.1 g / m < 2 >.

Next, the prepared metal-plated nanofibers are laminated on the adhesive layer formed on the first substrate.

Then, another low-melting-point polymer solution is discharged from the low melting point polymer unit or the epoxy resin-curing agent unit 10b through the nozzle to form another adhesive layer on the nanofiber layer, and the second substrate It is possible to produce an antibacterial nanomask by bonding.

 14 is a perspective view schematically showing a nozzle block installed in a low-melting-point polymer unit or an epoxy resin-curing agent 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. 5, 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.

17 and 20 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. 21 is arranged to face the longitudinal direction of the substrate, and Fig. 24 shows the shape arranged to face the width direction of the substrate.

On the other hand, the substrate is transferred to the rotation of the feed roller 3, which is operated by driving of a motor (not shown), and the auxiliary feed device 16, which is driven by the rotation of the feed roller 3.

It is also possible that the lamination device 100 is provided on the upper and lower surfaces of the nanofiber nonwoven fabric so as to bond the base material to the upper and lower surfaces of the nanofiber nonwoven fabric.

According to another preferred embodiment of the present invention, it is also possible to use a hot melt instead of the low melting point polymer or epoxy resin-curing agent.

The hot melt may be mixed with the polymer spinning solution, or a hot melt solution may be separately provided. Here, since the hot melt uses a polyvinylidene fluoride hot melt, it is possible to prevent the nanofibers from falling off the substrate together with the substrate. Thereafter, it is possible to manufacture an antibacterial nano-mask through a process of thermal fusion bonding in the laminating apparatus 90.

Example 1

A nanofiber web was prepared by using polyethylene terephthalate (PET) as a solute in a polymer spinning solution. That is, since polyethylene terephthalate (PET) has a high melting point and does not dissolve in a common solvent at room temperature, it uses a raw material named Co-PES of EMS, Switzerland as a solute. DMF and THF are used as a solvent, A spinning solution was prepared. As described above, the polymer spinning solution prepared by using THF and DMF as a solvent was stirred at room temperature for 24 hours at 25 DEG C to prepare a polymer spinning solution. The nanofiber web is manufactured by electrospinning with the polymer spinning solution and the manufactured nanofiber web is inserted into the laminated impeller, and then the laminated impeller is mounted in the bath. At this time, silver nitrate (AgNO 3 ) and 800 ml of water having a weight of 3 times the weight of the nanofiber web in the bath were dissolved in the bath and 200 ml of sodium hydroxide (NaOH) having a weight twice the weight of the nanofiber web weight After the addition, the stacked impeller is stirred at a low speed. At this time, the ammonia water is added while stirring, and then the mixture is added in a predetermined amount until it becomes transparent. After covering the bass lid on the body of the bass, a glucose reductant having a weight of 7.5 times the weight of the nanofiber web was charged, and the mixture was stirred at room temperature for 24 hours at 25 DEG C, and metal plating was performed on the nanofibers. The metal-plated nanofibers in the above-described manner are as shown in FIG.

Next, a low-polymerization-polyurethane having a softening temperature of 80-100 ° C was dissolved in a solvent of DMAc (N, N-dimethylaceticamide) in an amount of 15% by weight to prepare a low melting point polymer solution. And 10b, respectively.

It was laminated to the distance between the electrode and the collector in the low-melting polymer unit (10a) on the 40cm, an applied voltage 20kV, electrospinning and basis weight 0.1g / ㎡ the adhesive layer to a basis weight of 30g / m 2 substrate in a two-component 70 ℃, then The metal-plated nanofibers were laminated on the adhesive layer.

Another adhesive layer was formed on the metal-plated nanofibers under the same electrospinning conditions through the low-melting polymer unit 10b. A polyethylene terephthalate base having a basis weight of 150 g / m 2 was bonded to the metal-plated nanofibers through a joint device to finally prepare an antibacterial nano-mask.

Experimental Example 1

Evaluation of Antimicrobial Activity: The composite fabric prepared in Example 2 was cut to a width of X length and a length of 1 cm X 1 cm, and Escherichia coli, Staphylococcus aureus ATCC 12600 was cultured for 12 hours to evaluate antibacterial activity .

At this time, the cells were diluted to 1 × 10 ^ 6 CFU / ml, and the results are shown in Table 1 below.

division Strain unit Early After 10 minutes of curing (wash count 0) 50 times after washing Example 1 Escherichia coli CFU / ml 1X10 ^ 6
0 0 Staphylococcus aureus CFU / ml 1X10 ^ 6
0 0 Staphylococcus
aureus
ATCC 12600 CFU / ml 1X10 ^ 6 0 0

50 times washing (Washing): The cut specimens are placed in flowing tap water, immersed for 30 seconds, and washed and dried in a vacuum oven at 60 ° C.

[Table 1] shows that the antimicrobial activity after the lapse of 10 minutes showed an antimicrobial effect of 99.999% or more, and the antimicrobial effect was consistently excellent even after 50 times of washing (washing).

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: metal plating apparatus of nanofiber web, 3: nanofiber web,
10: Bath, 11: Bath body,
12: discharge part, 15: bath cover,
17: drive motor, 18: shaft,
30: Laminated impeller,
31, 31a, 31b: impeller case, 32: connecting rod,
32a: fastening portion, 32b: scrubber,
33: installation space, 34a: installation space,
34b: stopper, 35: pin hole,
37, 37 ', 37 ": impeller member, 38, 38', 38"
39: pinhole, 50: control part,
100: electrospinning device, 110, 110 ': unit,
111: nozzle block, 112: nozzle,
113: collector, 114: voltage generator,
115: substrate.

Claims (6)

Preparing nanofibers by electrospinning the polymer spinning solution;
Inserting the nanofibers into a stacked impeller, and then mounting a stacked impeller in a bath;
Dissolving the chemical plating solution and distilled water in the bath, adding sodium hydroxide (NaOH), and stirring the laminated impeller at a low speed;
Coating a bass lid on the body of the bass, adding a glucose reducing agent thereto, stirring the mixture, and performing metal plating to produce metal-coated nanofibers;
Depositing the metal-plated nanofibers on a first substrate; And
Laminating a second substrate on the metal plated nanofibers; ≪ RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the chemical plating solution comprises silver (Ag) or gold (Au). The method according to claim 1,
Wherein the adhesion between the metal-plated nanofibers and the first and second substrates is adhered through an adhesive layer formed by electrospinning a solution of a low melting point polymer or an epoxy resin-curing agent solution. The method of claim 3,
Wherein the low-melting-point polymer solution or the epoxy resin-curing agent solution is electrospinned on the entire surface or a part of the substrate and the metal-plated nanofiber. The method according to claim 3 or 4,
Wherein the low melting point polymer solution is one selected from the group consisting of a low melting point polyester, a low melting point polyurethane, and a low melting point polyvinylidene fluoride. The method according to claim 3 or 4,
Wherein the curing agent is one selected from the group consisting of an amine-based curing agent, an acid anhydride-based curing agent, and an imidazole-based curing agent.
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KR20210152664A (en) * 2020-06-09 2021-12-16 주식회사 케이에스씨 Personal breathing apparatus with negative and positive pressure adjustable structure
KR20220011425A (en) * 2020-07-21 2022-01-28 존 중원 김 Filter sheet for mask and triple structure mask with electromagnetic wave blocking and antibacterial function using this filter sheet
KR20220080967A (en) * 2020-12-08 2022-06-15 심기종 Manufacturing method of antibacterial mask with metal gild fiber
KR20230138114A (en) * 2022-03-23 2023-10-05 주식회사 블루인더스 Mask with antibacterial and antiviral performance

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JP4485264B2 (en) 2004-06-17 2010-06-16 名古屋メッキ工業株式会社 Electroless silver plating of aramid fiber material

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Publication number Priority date Publication date Assignee Title
KR20210152664A (en) * 2020-06-09 2021-12-16 주식회사 케이에스씨 Personal breathing apparatus with negative and positive pressure adjustable structure
KR20220011425A (en) * 2020-07-21 2022-01-28 존 중원 김 Filter sheet for mask and triple structure mask with electromagnetic wave blocking and antibacterial function using this filter sheet
KR20220080967A (en) * 2020-12-08 2022-06-15 심기종 Manufacturing method of antibacterial mask with metal gild fiber
KR20230138114A (en) * 2022-03-23 2023-10-05 주식회사 블루인더스 Mask with antibacterial and antiviral performance

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