KR20060022406A - A non-woven fabric composed of nanofiber with excellent water repellency and oil repellancy, and method of manufacturing for the same - Google Patents

Abstract

The present invention relates to a nanofiber nonwoven fabric having excellent water repellency and oil repellency, and a method for manufacturing the same, wherein the spinning solution, which is a polymer resin solution, is electrospun on a collector 7 under high voltage through a spinning nozzle 5 under high voltage. In manufacturing the nanofiber nonwoven fabric, the water-repellent agent was added to the spinning solution and mixed with the water-repellent agent, and the water resistance measured by the JIS L1092 B method was 1,000 mmH ₂ O or more, and the moisture permeability measured by the JIS L1099A-1 method. A nanofiber nonwoven fabric having a contact angle of 13,000 g / m 2/24 hours or more and a contact angle of 125 ° or more measured by the Sessil Drop method is prepared.

The present invention can simultaneously impart water repellency and oil repellency (moisture permeable waterproof performance) to the nanofiber nonwoven fabric in one process.

Nanofibers, non-woven fabrics, breathable waterproof, electrospinning, water repellent, oil repellent, water / oil repellent

Description

A non-woven fabric composed of nanofiber with excellent water repellency and oil repellancy, and method of manufacturing for the same             

1 is an electron micrograph showing a cross section of a polyurethane nanofiber nonwoven fabric prepared in Example 1 of the present invention.

Figure 2 is an electron micrograph showing an enlarged cross section of the polyurethane nanofiber nonwoven fabric prepared in Example 1 of the present invention.

      Figure 3 is an electron micrograph showing an enlarged surface of the polyurethane nanofiber nonwoven fabric prepared in Example 1 of the present invention.

Figure 4 is a schematic diagram of a bottom-up electrospinning apparatus used in Example 1 of the present invention.

Figure 5 is an electron micrograph showing the surface of the polyurethane nanofiber nonwoven fabric prepared in Comparative Example 1.

※ Explanation of main parts in drawings

1: Spinning solution main tank 2: Metering pump 3: Spinning solution drop device

4: Spinning nozzle block 5: Spinning nozzle 6: Nanofiber

7: Collector (conveyor belt) 8a, 8b: Collector support roller

9: Voltage generator 10: Radiation nozzle block left and right reciprocating device

11a: motor for agitator 11c 11b: non-conductive breaking device

11c: Stirrer 12: Spinner Discharge Device

13: transfer pipe 14: nonwoven fabric support roller

15: nonwoven fabric 16: nonwoven fabric winding roller

The present invention relates to a nanofiber nonwoven fabric having excellent water and oil repellency and a method for manufacturing the same, and more particularly, to add a water / oil repellent to the spinning solution when electrospinning a spinning solution which is a polymer resin solution. The present invention relates to a method of manufacturing a nanofiber nonwoven fabric having excellent water repellency and oil-repellency by mixing in a one-step process.

In the present invention, the nanofiber means a fiber having a fiber diameter of 1,000 nm or less.

In general, the conventional method of imparting water repellency and oil repellency to three-dimensional structures, ie, textiles, knitted fabrics, artificial leather, films, and other materials is the most widely used method of coating a coating liquid with a water-repellent agent added to the three-dimensional structure It is used. However, such a conventional coating method is very cumbersome in the process because it goes through a multi-step process.

On the other hand, conventional techniques for producing microfine fibers suitable for the production of artificial leather and the like is known as island-in-the-sea composite spinning, split composite spinning and blend spinning.

However, in the case of island-in-the-sea composite spinning or blend spinning, one of the two polymer components constituting the fibers must be eluted and removed for the finer fibers. In order to manufacture, there has been a problem of undergoing complex processes such as melt spinning, fiber manufacturing, nonwoven fabric production, urethane impregnation, and one component elution. Nevertheless, the two methods could not produce fibers with a diameter of 1,000 nm or less.

On the other hand, in the split type composite spinning method, two polymer components having different dyeing characteristics (for example, polyester and polyamide) coexist in the fiber, so that a dyeing band appears, and the artificial leather manufacturing process has a complicated problem. In addition, it was difficult to produce fibers with a diameter of 2,000 nm or less by the above method.

Water repellency and oil repellency are imparted to artificial leather made of the island-in-the-sea composite fiber manufactured by the island-in-the-sea composite spinning method or the blended composite fiber manufactured by the blend spinning method or the split composite fiber manufactured by the split composite spinning method. As described above, a method of coating the artificial leather with the coating liquid added with a water / oil repellent as described above is widely used, but in this case, the process is very complicated and a large amount of water / oil repellent is required to obtain a desired water repellency and oil repellency. Had to be added to the coating solution.

On the other hand, look at the manufacturing technology of the moisture-permeable waterproof foam can be roughly divided into three ways, the laminating method, dry method and wet method. A moisture-permeable waterproof cloth refers to a fabric that allows air to pass but does not allow water to pass through. First, Japanese Laid-Open Patent Publication No. H05-124144 describes a moisture-permeable waterproof sheet characterized by bonding a polyethylene porous film and a nonwoven fabric made of heat-adhesive fiber with heat and pressure. -213581 is a wear-resistant moisture-resistant waterproof cloth characterized in that the moisture-permeable film made of a polyamino acid-based polyurethane containing at least 0.1% powder of the reaction product of L- lysine and organic acid laminated on the fabric In Japanese Patent Laid-Open No. 2-47058, a resin composition made of an isocyanate compound, a hydrophobic organic solvent, a hydrophilic organic solvent, and water has a mixing ratio of hydrophilized polyamino acid urethane and polyurethane in a range of 10: 0 to 2: 8. A moisture-permeable waterproof fabric is described which is coated and dried onto a polyurethane adhesive.

Secondly, in the prior art of the dry method, Japanese Patent Application Laid-Open No. 4-249142 has a coating for forming a microporous coating on the fabric surface made of antistatic fiber, and the coating resin's inner layer contains a deodorizing substance and a coating film. A deodorant antistatic moistureproof waterproofing cloth having a porosity of 20 to 70% is described. Japanese Unexamined Patent Publication No. 4-146275 forms a porous moisture permeable membrane made of fluorine-modified polyurethane resin on the fiber surface, and is porous with an emulsion-based polyurethane resin polymer. A moisture-permeable waterproof fabric having a moisture-permeable membrane is described, and Japanese Patent Laid-Open No. 7-258971 describes the use of a cyclic compound for non-reducing maltooligosaccharides in a coating resin composition in coating processing of a dyed knit fabric using polyester fibers as a main component. A method of coating a polyester-based knitted fabric is described.

Lastly, in the prior art of the wet method, Japanese Patent Laid-Open No. 5-78984 uses a method of wet coating a polyurethane resin solution containing 1% or more of fine powder having an average particle diameter of 0.1 μm or less. It is prepared and has a moisture-permeable waterproof cloth having a moisture permeability of more than 7,000g / ㎡ / 24 hours and a water resistance of 0.6kg / ㎠ or more, and Japanese Patent Laid-Open No. Hei 8-13352 is coated with a polyurethane resin to the fabric, the porous resin layer having a porosity of 40% or more In this resin layer, a deodorizing moisture-permeable waterproof foam containing 1 to 40% by weight of fine powder having a deodorizing property of 1.5 µm or less is described.

The prior art (patent) described above consists of a method of forming fine pores in a film or membrane film which is not fibrous using a urethane resin or the like, so that the manufacturing method is very complicated and the pore distribution is also uneven.

An object of the present invention is to provide a water-repellent and oil-repellent property to the nanofibers during electrospinning to solve the conventional problems, so that the conventional coating process can be omitted so that the nanofiber non-woven fabric excellent in water repellency and oil repellency in one process To provide a method and a nanofiber nonwoven fabric produced by the above method.

The method of manufacturing the nanofiber nonwoven fabric of the present invention for achieving the above problems is the nanofiber by electrospinning the spinning solution, which is a polymer resin solution, on the collector 7 under high voltage through the spinning nozzle 5 under high voltage. In preparing the nonwoven fabric, the water-repellent agent is added and mixed with the spinning solution.

In addition, the nanofiber nonwoven fabric of the present invention prepared by the above method has a water pressure of 1,000 mmH ₂ O or more measured by the JIS L1092 B method, and a moisture permeability measured by the JIS L1099A-1 method of 13,000 g / m 2/24 hours or more, Cecil The contact angle measured by the drop (Sessil Drop) method is characterized in that more than 125 °.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

First, looking at the method of manufacturing a nanofiber nonwoven fabric according to the present invention, the collector 7 is subjected to a high voltage through the spinning nozzle 5 is a high voltage is applied to the spinning solution which is a polymer resin solution in the electrospinning apparatus such as FIG. When the nanofibers are prepared by electrospinning onto the water, a water- and oil-repellent agent is added to the spinning solution and mixed to give nanofibers with excellent water and oil repellency.

4 is a schematic diagram of a bottom-up electrospinning apparatus.

The water- and oil-repellent agent is any compound containing fluoride, specifically, a group consisting of a monomer containing fluorine, an oligomer containing fluorine, a polymer containing fluorine, a copolymer containing fluorine, and mixtures thereof It is 1 type, or 2 or more types of compounds chosen from.

Specific examples of the water / oil repellent include N-bis (2-hydroxyethyl) perfluorobutylsulfonamide], 1,4-bis (1-hydroxy-1,1- Dihydroperfluoropropoxy) perfluorouro-n-butane [1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane], 2- (N-methylperfluorourobutane Sulfonamido) ethanol [2- (N-methylperfluorobutanesulfonamido) ethanol], perfluorooctanesulfonylfluoride, and the like.

The addition amount of the water- and oil-repellent agent is 0.01 to 30% by weight, more preferably 0.01 to 10% by weight relative to the weight of the polymer resin in the spinning solution.

If the content of the water / oil repellent exceeds 30% by weight, the formation ability of the nanofibers may be remarkably deteriorated during electrospinning, and thus, the electrospinning may be difficult. If the water repellent is less than 0.01% by weight, the nanofibers may be water-repellent and oil-repellent. The effect is minimal.

On the other hand, as the electrospinning method, (i) a bottom-up electrospinning method in which the radiation nozzle block 4 is located below the collector 7, and (ii) the radiation nozzle block 4 is located above the collector 7. Although any of the top-down electrospinning method and (i) the horizontal electrospinning method in which the radiation nozzle block 4 and the collector 7 are positioned at a horizontal or similar angle, the bottom-up electrospinning method is more preferable. .

The reason is that in the case of the bottom-up electrospinning method, the nozzles can be arranged indefinitely so that mass production is possible and the width or thickness of the nonwoven fabric can be freely adjusted.

The polymer spinning solution may include a polyester resin, a nylon resin, a polysulfone resin, a polylactic acid, chitosan, collagen, cellulose, fibrinogen, a copolymer thereof, a mixture thereof, or a sol-gel containing a metal component (Sol-gel). ).

As described above, when the water-repellent agent is added to and mixed with the spinning solution during electrospinning, the uniformity is excellent and the specific surface area is very wide. Therefore, even when a small amount of the water-repellent agent is added, the water-repellent and oil-repellent properties are imparted to the nanofibers. can do.

The nanofiber nonwoven fabric of the present invention prepared as described above may not allow water to pass through and may be used as a material for various moisture-permeable tarpaulins, ultra-high performance filter materials, artificial leather, and various food and beverage packaging materials by passing through air. It is useful for all industries such as wiper material, medical and clothing.

Next, look at the method of manufacturing the nanofiber nonwoven fabric of the present invention using the bottom-up electrospinning apparatus of FIG.

First, the thermoplastic resin or thermosetting resin spinning solution stored in the spinning solution main tank 1 is metered by the metering pump 2 and supplied to the spinning solution drop device 3 in a quantitative manner. In this case, the thermoplastic or thermosetting resin for preparing the spinning solution may be polyester resin, acrylic resin, phenol resin, epoxy resin, nylon resin, poly (glycolide / L-lactide) copolymer, poly (L-lactide) resin, Polyvinyl alcohol resin, polyvinyl chloride resin and the like can be used. As the spinning solution, any of the above resin melts or solutions may be used.

In this way, the spinning solution supplied into the spinning solution drop device 3 is discontinuously passing through the spinning solution drop device 3, that is, the clouding of the spinning solution is blocked more than once, and a high voltage is applied to the spinning solution 11c. Is supplied to the installed spinneret block (4). The spinning solution drop device (3) also serves to block the flow of spinning solution to prevent electricity from flowing in the spinning solution main tank (1).

Subsequently, in the spinning nozzle block 4, the spinning liquid is discharged upward through the upward spinning nozzle 5 to the upper collector 7 where the high voltage is applied, thereby manufacturing the nonwoven web.

At this time, the excess spinning solution supplied to the top of the nozzle block is forcibly transferred to the spinning solution main tank 1 by the spinning solution discharge device (12).

At this time, in order to promote the formation of fibers by the electric force, the radiation nozzle block 4 and the collector 7 are subjected to a voltage of 1 kV or more, more preferably 20 kV or more, generated by the voltage generator 9. It is more advantageous in terms of productivity to use an endless belt as the collector 7. The collector 7 preferably reciprocates a certain distance from side to side to make the density of the nonwoven uniform.

When the nonwoven fabric formed on the collector 7 is wound on the winding roller 16 via the nonwoven fabric support roller 14, the nonwoven fabric manufacturing process is completed.

Meanwhile, two or more kinds of polymer spinning solutions may be electrospun on one collector 7 through different nozzles 5 arranged on one spinning nozzle block 4, and two or more kinds of polymer spinning solutions may be used. They may be electrospun on one collector 7 through nozzles 5 arranged on two or more separate spinning nozzle blocks 4, respectively.

In this case, the water- and oil-repellent agent may be added and mixed to all of the two or more polymer spinning solutions, respectively, or the water- and oil-repellent agent may be added and mixed only to some of the spinning solutions.

The nanofiber nonwoven fabric produced by the manufacturing method of the present invention described above has a water resistance of 1,000 mmH ₂ O or more measured by the JIS L1092 B method, and a water vapor transmission rate measured by the JIS L1099A-1 method of 13,000 g / m 2/24 hours or more. , Contact angle measured by Sessil Drop method is more than 125 °.

More preferably, the water pressure is 6,000 mmH ₂ O or more, the moisture permeability is 15,000 g / m 2/24 hours or more, and the contact angle is 135 ° or more.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited only to the following examples.

Example 1

A solution was prepared by dissolving a polyurethane resin having a number average molecular weight of 80,000 in N, N-dimethylformamide in 8 parts by weight, and then N-bis (2-hydroxyethyl) perfluorourosulfonamide (water repellent) in this solution. -Oil Repellent) A spinning solution was prepared by adding 60 parts by weight of a solution dispersed in dimethylformamide to 3 parts by weight of a polyurethane solution to a polyurethane solution. The prepared spinning solution was measured using a rheometer (Rheometer-DV, III, Brookfield Co., USA), and the viscosity was 565 centipoas. The conductivity is also 0.29 mS / m, as measured by a conductivity meter (CM-40G, TOA electronics Co., Japan). The spinning solution was electrospun in a bottom-up electrospinning manner as shown in FIG. 4 to prepare nanofibers. While storing the spinning solution in the spinning solution main tank (1), the metering pump (2) is quantitatively metered and supplied to the spinning solution drop device (3) to discontinuously switch the flow of spinning solution. Subsequently, the spinning solution was supplied to the spinning nozzle block 4 subjected to a voltage of 35 kV, and spun upward through the nozzle to a fiber shape, and was integrated on the collector 7 located at the top, and the width was 60 cm and the weight was 10.0. A nonwoven fabric of g / m 2 is produced. The spinning nozzles arranged in the spinning nozzle block used were arranged diagonally, and the number of spinning nozzles was 6,000 holes. Spinning distance was 20 cm. The discharge amount of one hole of the spinning nozzle was spun at 3 mg / min. The reciprocating motion of the spinneret block was 4 m / min, and the nonwoven fabric production speed was 3 m / min. During the spinning process, the solution overflowing the top of the spinning nozzle block was forcibly transferred to the storage tank using suction air.

The thickness of the nanofiber nonwoven fabric prepared as described above was 167 μm, the water pressure measured by the JIS L1092B method was 10,000 mmH ₂ O, and the water vapor transmission rate measured by JIS L1099A-1 was 21,000 g / m 2/24 hours, and cecil drop (Sessil The contact angle measured by the drop method (SEO, Korea) was 144 °. FIG. 1 is an electron micrograph showing a cross section of a nonwoven fabric prepared in Example 1, which includes a large number of pores, and FIG. 2 is an enlarged electron microscope photograph of FIG. Figure 3 is an electron micrograph showing the surface of the prepared nonwoven fabric is very uniform fiber diameter.

Comparative Example 1

A nanofiber nonwoven fabric was prepared in the same manner as in Example 1 except that the water- and oil-repellent agent was not added and mixed with the spinning solution.

As a result of measuring the physical properties of the nanofiber nonwoven fabric prepared as described above, the water resistance measured by the JIS L1092B method is 1,000mmH ₂ O, the water vapor transmission rate measured by JIS L1099A-1 is 12,200g / ㎡ / 24 hours, Cecil drop (Sessil The contact angle measured by the drop method (SE0, Korea) was 119 ° and the thickness was 165 μm. Figure 5 is an electron micrograph showing the surface of the nonwoven fabric prepared in Comparative Example 1 can be seen that the fiber diameter is non-uniform and the diameter is increased than Example 1.

The present invention can omit the coating step of imparting water repellency and oil repellency to a nonwoven fabric or the like, thereby simplifying the process.

Specifically, the present invention provides a nanofiber nonwoven fabric having excellent water and oil repellency in a one-step process by imparting water repellency and oil repellency to nanofibers during electrospinning.

Nanofiber nonwoven fabric of the present invention has the advantage of excellent moisture permeability.

Claims (12)

In the production of nanofiber nonwoven fabric by electrospinning the spinning solution, which is a polymer resin solution, on the collector 7 under high voltage through a spinning nozzle 5 under high voltage, a water / oil repellent is added to the spinning solution. A method for producing a nanofiber nonwoven fabric having excellent water and oil repellency, characterized by mixing. The compound according to claim 1, wherein the water / oil repellent agent is selected from the group consisting of monomers containing fluorine, oligomers containing fluorine, polymers containing fluorine, copolymers containing fluorine and mixtures thereof A method for producing a nanofiber nonwoven fabric having excellent water and oil repellency. The method of claim 1, wherein the water- and oil-repellent agent in the spinning solution is 0.01 to 30% by weight based on the weight of the polymer resin. The method of manufacturing a nanofiber nonwoven fabric having excellent water and oil repellency, characterized in that the content of the water- and oil-repellent agent in the spinning solution is 0.01 to 10% by weight based on the weight of the polymer resin. 2. The electrospinning method according to claim 1, wherein the electrospinning method is (i) a bottom-up electrospinning method in which the spinneret block 4 is located below the collector 7, and (ii) the spinneret block 4 is located on top of the collector 7; Water-repellent and oil-repellent, characterized in that the one is selected from the top-down electrospinning method and (i) the horizontal electrospinning method in which the radial nozzle block (4) and the collector (7) is located at a horizontal or similar angle Excellent nanofiber nonwoven fabric manufacturing method. The sol-gel according to claim 1, wherein the polymer spinning solution is polyester resin, nylon resin, polysulfone resin, polylactic acid, chitosan, collagen, cellulose, fibrinogen, copolymers thereof, mixtures thereof or sol-gels containing metal components (Sol). -gel) nanofiber nonwoven fabric excellent in water and oil repellency, characterized in that consisting of. 2. The water repellent property according to claim 1, characterized in that two or more kinds of polymer spinning solutions are electrospun on one collector 7 through different nozzles 5 arranged on one spinning nozzle block 4 respectively. Nanofiber nonwoven fabric with excellent oil repellency. 2. The water repellent property according to claim 1, wherein two or more kinds of polymer spinning solutions are electrospun on one collector 7 through nozzles 5 arranged on two or more separate spinning nozzle blocks 4, respectively. Nanofiber nonwoven fabric with excellent oil repellency. Prepared by the method of claim 1, the water pressure measured by the JIS L1092 B method is 1,000mmH ₂ O or more, the water vapor transmission rate measured by the JIS L1099A-1 method is 13,000g / ㎡ / 24 hours or more, by the Sessil Drop method Nanofiber nonwoven fabric with excellent water and oil repellency, characterized in that the measured contact angle is 125 ° or more. 10. The nanofiber nonwoven fabric having excellent water and oil repellency according to claim 9, wherein the water pressure is 6,000 mmH ₂ O or more. 10. The nanofiber nonwoven fabric having excellent water and oil repellency of claim 9, wherein the water vapor transmission rate is 15,000 g / m 2/24 hours or more. 10. The nanofiber nonwoven fabric having excellent water and oil repellency according to claim 9, wherein the contact angle is 135 degrees or more.

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