KR100905501B1 - Nano-Fiber Composite Sheet with Moisture-Absorption and Quick-Drying Capability - Google Patents

Abstract

The present invention relates to a composite sheet composed of a multi-functional nanofiber layer having a moisture-absorbing quick-drying function, by combining two or three nanofiber layers and microfiber layers having different densities due to differences in diameter distribution, Provided is a composite sheet having moisture absorption and ultrafast drying characteristics and a method for producing the same.

Composite sheet composed of the multi-functional nanofiber layer of the present invention has a waterproof function, one-way moisture transition, super-absorbent, ultra-fast drying performance can be applied to various industrial fields such as industrial, medical, sports, clothing.

Nanofiber, Hygroscopic quick drying, Density difference, Composite sheet, Multi-layer structure, Electrospinning

Description

Nano-Fiber Composite Sheet with Moisture-Absorption and Quick-Drying Capability}

The present invention relates to a hygroscopic quick-drying composite sheet (1) composed of nanofibers, and more particularly, selected from high density nanofiber layers (100), low density ultrafine fiber layers (200), and microfiber layers (300) having different average fiber diameters. A composite sheet composed by complexing a species or three into a double tissue or a triple tissue.

Vinyl or film such as a conventional raincoat does not pass the rain, but sweat or water vapor had a disadvantage that does not pass. The moisture-permeable waterproof material is a functional fiber that overcomes these shortcomings. It is a functional fiber that allows small particles, such as water vapor and sweat, to pass 0.4 nm in size, such as water vapor and sweat, without passing through large water particles, such as raindrops and water droplets. . Recently, development and research on functional fibers having moisture-permeable waterproof properties and moisture-absorbing quick-drying performance are actively underway.

For the development of hygroscopic quick-drying material, a lot of research has been conducted, such as the method of controlling or compounding the structure of the fabric as well as the fiber itself, the most common method is to use the capillary phenomenon. That is, a method of using a hollow fiber having fine pores on the surface of the fiber, or by compounding a fiber having a groove (slit) structure to exhibit a capillary phenomenon is generally used.

In addition, a method of using a natural fiber having excellent hygroscopicity, a microfiber yarn, and a sectional cross-section yarn to have a moisture absorption quick-drying performance is generally used.

Korean Unexamined Patent Application Publication No. 2002-12828 describes technical matters related to circular knitted fabrics using a sectional cross-section yarn and a hydrophobic yarn, and Japanese Unexamined Patent Publication No. 3-213546 proposes an absorbent sheet using a density difference. Patent 10-0486881 also proposes a hygroscopic quick-drying fabric having a double structure in which a hydrophobic yarn and a natural fiber are composited using density differences.

However, in the case of the inventions, because the diameter of the yarn used is composed of a relatively large range of about 10 ~ 100 ㎛ not only does not have sufficient moisture absorption quick-drying performance, but also has the disadvantage that additional processing is required for the waterproof function. there was.

In addition, in the method for producing a fiber laminate having a nanofiber layer described in Korean Patent Laid-Open Publication No. 10-2007-0047873, two or more different types of nanofibers may be alternately repeated or randomly stacked, and this may be used as a filter medium, but the density Since there is no limit to expecting the moisture absorption quick-drying performance by the capillary phenomenon because there is no distinction of the difference, there is a problem that a secondary additional treatment is required to give the moisture absorption quick-drying performance.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is selected from two kinds of high density nanofiber layer 100, low density ultrafine fiber layer 200 and micro fiber layer 300 having different fiber diameters or Three types are combined to provide a composite sheet having superabsorption and super fast drying performance organized in double or triple.

Another object of the present invention is to provide a composite sheet provided with a waterproof function, or a composite sheet of which moisture absorption and quick drying performance are maximized.

Still another object of the present invention is to provide a composite sheet having functionalities such as antibacterial properties, unidirectional heat transfer properties, drug delivery properties, and the like.

In order to achieve the above object, one aspect of the present invention provides an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm, with one surface and an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm. Provided is a hygroscopic quick-drying composite sheet in which one surface of a phosphorus low density ultrafine fiber layer is combined.

The second aspect of the present invention for achieving the above object is that one side of the high density nanofiber layer having an average fiber diameter of 50 to 500 nm and basis weight 20 to 100 gsm and one side of the micro fiber layer having an average fiber diameter of 1000 to 20000 nm Provided is a complex moisture-absorbing quick-drying composite sheet.

A third aspect of the present invention for achieving the above object is a composite of one side of a low density ultra-fine fiber layer having an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm, and one side of a micro fiber layer having a fiber diameter of 1000 to 20000 nm. To provide a hygroscopic quick-drying composite sheet.

A fourth aspect of the present invention for achieving the above object is a high-density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm, and a fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm. Provided is a moisture-absorbing quick-drying composite sheet in which a low density ultrafine fiber layer and a microfiber layer having a fiber diameter of 1000 to 20000 nm are sequentially combined.

According to one embodiment, the moisture-absorption quick-drying composite sheet further includes a moisture-permeable waterproof material.

According to another embodiment, the surface of the hygroscopic quick-drying composite sheet is chemically treated, corona discharged, or plasma treated.

According to another embodiment, the hygroscopic quick-drying composite sheet further includes a hydrophilic material.

According to another embodiment, the high-density nanofiber of the hygroscopic quick-drying composite sheet further includes one or more of silver nitrate, silver nanoparticles, titanium dioxide, natural extracts or far-infrared radiating material.

The present invention is to provide a composite sheet having a super-absorbent, ultra-fast drying characteristics by capillary action, and a manufacturing method thereof by compounding two or three kinds of nanofiber layers and microfiber layers having different diameter distributions and density differences. Along with this, one-way water transition, super absorption, and quick drying effect can be obtained.

In particular, the composite sheet prepared as described above has a water resistance of 300 to 30000 mmH ₂ O, and a moisture permeability of 13000 g / m 2 24 Hrs or less.

In addition, in the production of the nanofibers, the spinning solution contains functional materials such as silver nitrate (AgNO ₃ ), silver nanoparticles, natural extracts, drugs, and various far-infrared emitters, and thus, unidirectional heat transfer, drug transfer, and the like. There is an effect that can provide a composite sheet having versatility.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

One aspect of the present invention is one side of a high density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm, and one side of a low density ultrafine fiber layer having an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm. The present invention relates to a complexed hygroscopic quick-drying composite sheet.

Although the thickness of the high density nanofiber layer and the ultrafine fiber layer is not particularly limited, it is preferably 5 to 200 μm, and the total thickness of the two layers does not exceed 300 μm. When the layer thickness is 5 μm or more, the strength as the fiber layer becomes sufficient, and the absorption quick-drying property can be secured, and when it is 200 μm or less, a soft touch can be maintained.

The second aspect of the present invention is a hygroscopic quick-drying composite sheet in which one surface of a high density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm and one surface of a micro fiber layer having an average fiber diameter of 1000 to 20000 nm are combined. It is about.

The thickness of the high-density nanofiber layer is as described above, and the thickness of the microfiber layer is not particularly limited, but is preferably 100 to 500 µm. When the thickness of the microfiber layer is 100 μm or more, the function as a support layer can be sufficiently exhibited, and when the thickness of the micro fiber layer is 500 μm or less, moisture absorption and dryness can be exhibited while maintaining a comfortable fit.

A third aspect of the present invention relates to a hygroscopic quick-drying composite sheet in which one side of a low density ultra-fine fiber layer having an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm and one side of a micro fiber layer having a fiber diameter of 1000 to 20000 nm are combined. will be.

The thickness of the low density ultrafine fiber layer and the thickness of the micro fiber layer are as described above.

A fourth aspect of the present invention is a high density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm, a low density ultrafine fiber layer having a fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm, and a fiber diameter. The moisture-absorption quick-drying composite sheet in which the microfibrous layer of 1000 to 20000 nm is sequentially combined.

The thickness of the high density nanofiber layer, the thickness of the low density ultra-fine fiber layer and the thickness of the micro fiber layer are as described above.

The high-density nanofibrous layer 100 is prepared by electrospinning a thermosetting or thermoplastic polymer as a raw material, and the fiber has a diameter of 50 to 500 nm and has a basis weight in the range of 20 to 100 gsm.

Thermosetting or thermoplastic polymers which are preferably used for producing the high-density nanofibrous layer through the electrospinning, polyurethane (PU), polyacrylonitrile (PAN), nylon (Nylon), polylactic acid (PLA), Polycarbonate (PC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polystyrene (PS), polyvinylcarbazole (PVC), poly Vinylpyridine (PVP), polyamide, polybenzylimidazole (PBI), polyethylene terephthalate (PET), polyester (PE) and the like may be used alone or in combination.

 The high-density nanofibrous layer prepared by electrospinning as described above has a large specific surface area to volume ratio, and has a characteristic of blocking the passage of viruses, bacteria, and micro-contaminants.

The low density ultra-fine fiber layer 200 refers to a fiber produced by a technique such as electrospinning, melt-blown, flash spinning, conjugate spinning, etc., the low density ultra-fine fiber layer The average diameter is preferably 500 to 3000 nm and basis weight is 5 to 30 gsm. The cross-sectional shape of the low-density ultra-fine fibers is composed of a circular or hetero-cross section yarn, it is desirable to have a function of quickly spreading and transferring the moisture absorbed from the high-density nanofiber layer to the outermost layer.

Thermosetting or thermoplastic polymers which are preferably used to prepare the low density ultrafine fiber layer include polyurethane (PU), polyacrylonitrile (PAN), nylon (Nylon), polylactic acid (PLA), and polycarbonate (PC). ), Polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVdF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polystyrene (PS), polyvinylcarbazole (PVC), polyvinyl piolidine ( PVP), polyamide, polybenzylimidazole (PBI), polyethylene terephthalate (PET), polyester (PE) and the like may be used alone or in combination.

The microfiber layer 300 may be manufactured using a conventional fabric, a nonwoven fabric or a DuPosted fabric having a moisture permeability, such as Gore-Tex, having a fiber diameter of 1.0 to 20 μm, and blocking a large pollutant source. , It is preferable to use those composed of natural fibers or synthetic fibers provided with elongation to protect the nanofiber layer from external stimuli.

In the manufacture of the moisture-absorption quick-drying composite sheet of the present invention, the composite of sheets having different fiber diameters and densities can be prepared using a conventional fabrication method, preferably thermal bonding, ultrasonic bonding, laser irradiation, high frequency. Processing, waterjet, and the like.

The moisture-absorbing quick-drying composite sheet of the present invention may further include a moisture-permeable waterproof material such as, for example, Gore-Tex or dry zone. This is possible by a post-processing treatment by a lamination method or a coating method, and through this, a waterproof function can be given.

Hygroscopic quick-drying composite sheet of the present invention can impart a hydrophilic function to the surface by using a chemical treatment, corona discharge, plasma treatment,

In addition, a hydrophilic function can also be imparted using, for example, a method of performing cross-sectional absorption processing on a hydrophilic material such as a polyamino acid resin by a roller, knife coating, spray method or the like.

The moisture-absorbing quick-drying composite sheet of the present invention may further include silver nitrate, silver nanoparticles, titanium dioxide, natural extracts, far-infrared radiating materials, etc., in the production of the high density nanofibers. This is achieved by dissolving and dispersing the material in the spinning solution of the polymer and spinning them together so that functional nanoparticles such as silver nanoparticles or titanium dioxide particles are fixed on the surface of the polymer nanofibers, and thus antibacterial, far-infrared radiation, unidirectional heat transfer, It is possible to obtain a composite sheet to which effects such as deodorization and deodorization are imparted.

Here, the natural extract is preferably selected from the group consisting of cypressaceae phytoncide of pineaceae, cinnamon of camphor, catechin of camellia, herb of rosaceae.

Here, the far-infrared radiating material is preferably selected from the group consisting of ocher, elvan, charcoal or activated carbon, and ceramics.

The compounding of the hygroscopic quick-drying composite sheet of the present invention is accomplished by one or more of thermal bonding, ultrasonic bonding, laser irradiation or high frequency treatment, and waterjet.

The moisture-absorption quick-drying composite sheet produced according to the present invention has a water resistance of 300 to 30000 mmH ₂ O and a moisture permeability of 13000 g / m 2 24 Hrs or less. If the water pressure and moisture permeability are within the above range, it is suitable for performing a sufficient waterproof function.

As the physical properties of the composite sheet according to the present invention, the degree of waterproofing, moisture permeability, drying rate and the like were evaluated using the following method and summarized in Table 1.

As the water pressure indicating the degree of waterproofing, low pressure method according to KS K0591-1999 and JIS-L 1096 was used.

The measurement of moisture permeability was evaluated using KS K 0594-1988, ASTM E 96-80 (g / m2 24hrs) and JIS-L 1099 method, and the higher the value, the better the moisture permeability.

The drying rate was measured using visual discrimination. Samples were taken at 15 cm in length and width at standard conditions, and 10 g of water was poured on the back of the sample, and the time was measured until the back layer was completely dried.

Hereinafter, with reference to the accompanying drawings, a composite sheet manufacturing method consisting of a multifunctional nanofiber layer having a moisture absorption quick-drying function according to the present invention will be described in detail. However, the present invention is not limited only to the following examples.

Example 1

Average fiber diameter of 300 nm, fiber density of 1.15 g / cm ³ , basis weight of 30 gsm, electrospun polyacrylonitrile (PAN) -based high density nanofibrous layer 100 and average fiber diameter of 50 to 100 μm After heat treatment of the electrospun polystyrene (PS) low density ultrafine fiber layer (200) consisting of 2000 nm (2.0 μm), density 0.9 g / cm ³ , basis weight 15 gsm, and thickness of 50-100 μm 1 to prepare a composite sheet having a double structure as shown in b of Figure 1 to evaluate the physical properties.

The spinning solution was prepared by dissolving 10% by weight of PAN in DMF during spinning of the nanofibers.The spinning solution was connected to the spinneret, and the electrospinning was carried out with an applied voltage of about 50 kV and a distance of 30 cm between the spinneret and the current collector. Carried out. Scanning electron micrographs and diameter distributions of the emitted PAN nanofibers are shown in FIG. 3. Most of the electrospun nanofibers were in the range of less than 500 nm in diameter and consisted of an average of 200 nm.

The low density ultrafine fiber layer was prepared by dissolving PS in DMF at 20% by weight and electrospinning in the same manner as described above. 4 shows a scanning electron micrograph of the electrospun PS fiber, and the average fiber diameter was about 2 μm, which was about 10 times larger than that of the PAN fiber of the high density nanofiber layer.

Example 2

The woven fabric woven from a polypropylene (PP, polypropylene) microfiber layer having an average diameter of 20 μm to a PS layer (low density ultrafine fiber layer) having an average fiber diameter of 2 μm manufactured by the method of Example 1 was used in FIG. Composite sheets of a double structure such as c were prepared to evaluate physical properties. 5, the cross-sectional structure of the manufactured composite sheet was shown using the scanning electron microscope.

Example 3

In the same manner as in Example 1, polylactic acid (PLA, polylaticacid) -based nanofibers were electrospun so as to have a basis weight of 50 gsm (FIG. 6), and as a low density ultrafine fiber layer, PET (polyethyleneterepthalate) The composite sheet was fabricated so that the woven fabric of the) -type cross-section yarn was made into a double structure as shown in FIG.

Example 4

PET composite woven fabric (micro fiber layer) having a diameter of 20 μm on the composite sheet prepared by the method of Example 1 was prepared using a thermal bonding method to prepare a composite sheet having a triple structure as shown in FIG. .

Comparative Example 1

Water-resistant pressure against a composite fabric produced by combining a high-density hydrophobic polyolefin yarn having a process water content of 0.05 to 1% and a natural fiber (cotton) having a process water content of 8% or more with an average fiber diameter of 20 µm in the same thickness as in Example 1. Table 1 shows the results of measuring the moisture permeability and drying rate in comparison with Examples 1 to 5.

TABLE 1

division Water pressure resistance (mmH2O) Moisture permeability (g / ㎡24hrs) Drying speed (min) Example 1 300 10000 1.5 Example 2 10000 6000 3.5 Example 3 15000 3000 4.5 Example 4 30000 13000 2.5 Example 5 10000 10000 4.0 Comparative Example 1 400 6500 10.0

Example 5

After adding DMF (dimethyformamide) and THF (tetrahydrofuran) solvent to the polyurethane (PU) to a concentration of 15% by weight, 5% by weight of silver nitrate (AgNO ₃ ) was added to dissolve at room temperature to prepare a spinning solution. The high-density nanofiber layer 100 was obtained by electrospinning such that the basis weight was 30 gsm and the average fiber diameter was 300 nm.

A low density polyethylene (LDPE, low-density polyethylene) on the nanofibrous layer was melt blown (melt-spun spinning) method to produce a nonwoven fabric having an average fiber diameter of 5 μm using a thermal bonding method as shown in FIG. A composite sheet composed of a fiber layer / micro fiber layer was obtained.

The composite sheet thus prepared was cut 1 cm in diameter and length, and then cultured for 12 hours with Staphylococcus aureus ATCC 12600, known as Escherichia coli, Staphylococcus aureus, and purulent bacteria, to evaluate their antibacterial properties.

At this time, the cells were diluted to 1 × 10 ⁶ CFU / mL and used, and the results are shown in Table 2. After 10 minutes and 50 washes (washing), the antimicrobial effect was confirmed to be maintained at 99.999% or more.

Comparative Example 2

The composite sheet was obtained in the same manner as in Example 5 except that silver nitrate was added, and the results of the evaluation of the antibacterial properties in the same manner as in Example 5 are shown in Table 2.

TABLE 2

Strain unit Concentration Rate of bacteriostatic reduction after 10 minutes (0 washes) Reduction of bacteriostaticity after 50 washes (%) Example 5 Comparative Example 2 Example 5 Comparative Example 2 S. Aureus ATCC 12600 CFU / ml 1 x 10 ⁶ 99.99 0 99.99 90 Escherichia coli CFU / ml 1 x 10 ⁶ 99.99 0 99.99 85 Staphylococcus aureus CFU / ml 1 x 10 ⁶ 99.99 0 99.99 50

* Washing 50 times (washing): Place the cut specimen in running tap water and soak for 30 seconds and repeat the washing and drying in a vacuum oven at 60 ℃.

1 is a schematic view of a cross section of a composite sheet prepared by the present invention, (a) and (b) is a high density nanofiber layer / low density ultrafine fiber layer, (c) is a low density ultrafine layer / microfiber layer, (d) is a high density nanofiber layer / Microfiber layer, (e) represents a high-density nanofiber layer / low density ultra-fine layer / microfiber layer, respectively.

It is a schematic diagram which shows the moisture absorption quick-drying mechanism of this invention.

3 shows a scanning electron micrograph (a) and diameter distribution (b) of the electrospun PAN nanofibers.

Figure 4 shows a scanning electron micrograph of PS ultrafine fibers having an average diameter of 2 microns electrospun.

Figure 5 shows a cross-sectional scanning electron micrograph of the composite nanofiber bonded to the electrospun PU and PP woven fabric.

Figure 6 shows a scanning electron micrograph of the electrospun polylactic acid-based nanofibers.

Claims (11)

Hygroscopic quick-drying composite sheet in which one surface of a high density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm and one surface of a low density ultrafine fiber layer having an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm . A moisture absorption quick-drying composite sheet in which one surface of a high density nanofiber layer having an average fiber diameter of 50 to 500 nm and a basis weight of 20 to 100 gsm and one surface of a micro fiber layer having an average fiber diameter of 1000 to 20000 nm are combined. A moisture-absorbing quick-drying composite sheet in which one surface of a low density ultra-fine fiber layer having an average fiber diameter of 500 to 3000 nm and a basis weight of 5 to 30 gsm and one surface of a micro fiber layer having a fiber diameter of 1000 to 20000 nm are combined. High density nanofiber layer having an average fiber diameter of 50 to 500 nm and basis weight of 20 to 100 gsm, a low density ultrafine fiber layer having a fiber diameter of 500 to 3000 nm and basis weight of 5 to 30 gsm, and a micrometer having a fiber diameter of 1000 to 20000 nm Moisture-absorbing quick-drying composite sheet in which the fiber layers are composited in order. The moisture absorption quick-drying composite sheet according to any one of claims 1 to 4, wherein the moisture-absorption-drying composite sheet includes a moisture-permeable waterproof material. The moisture absorbing quick dry composite sheet according to any one of claims 1 to 4, wherein the surface of the moisture absorbing quick dry composite sheet is chemically treated, corona discharge, or plasma treated. The moisture absorbent quick dry composite sheet according to any one of claims 1 to 4, wherein the moisture absorbent quick dry composite sheet includes a hydrophilic material. The moisture-absorbing quick-drying composite sheet according to any one of claims 1, 2 and 4, wherein the high-density nanofibers include at least one of silver nanoparticles, titanium dioxide, natural extracts, or far-infrared radiating materials. The moisture absorption quick-drying composite sheet according to any one of claims 1 to 4, wherein the complexing is performed by at least one of thermal bonding, ultrasonic bonding, laser irradiation, water jet, or high frequency treatment. The moisture absorption quick-drying composite sheet according to any one of claims 1 to 4, wherein the water resistant pressure of the composite sheet is 300 to 30000 mmH ₂ O, and the moisture permeability is 13000 g / m 2 24 Hrs or less. The hygroscopic quick-drying composite sheet according to any one of claims 1, 3 and 4, wherein the low-density ultra-fine fiber layer is prepared by using alone or a combination of electrospinning, melt spray spinning, or flash spinning techniques.

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