KR101070421B1 - Nano fiber coated fiber structure for waterproof and berathable, and method for making thereof - Google Patents

Abstract

 The present invention relates to a water-permeable waterproof fiber structure and a method for manufacturing the same, wherein a nanofiber coating layer having micropores is formed by electrospinning a polymer spinning solution containing a photoinitiator on the surface of the fiber structure, wherein the nanofiber coating layer is irradiated with ultraviolet rays. The present invention relates to a moisture-permeable waterproof fiber structure coated with nanofibers having excellent moisture permeability and waterproofness, and a method of manufacturing the same, bonded to the fiber structure.

Breathable waterproof, fiber structure, nanofiber, electrospinning, photoinitiator

Description

Nanofiber-coated moisture-permeable fiber structure and manufacturing method thereof {NANO FIBER COATED FIBER STRUCTURE FOR WATERPROOF AND BERATHABLE, AND METHOD FOR MAKING THEREOF}

 The present invention relates to a water-permeable waterproof fiber structure and a method of manufacturing the same, and a nanofiber-coated layer having a porous nanofiber coating layer formed on the surface of the fiber structure, and having a good moisture-permeable and waterproof property.

In general, the moisture-permeable waterproof fiber structure has excellent moisture permeability and waterproofness by forming a coating layer on the fiber structure so that raindrops of 100 μm do not pass into the fiber from the outside of the fiber and 0.004 μm of moisture released from the body can flow out of the fiber in the fiber. It refers to a fiber structure used for sportswear, military uniforms, tents and the like.

Conventionally, a method of providing a moisture-permeable waterproof function to a fiber structure is a polyurethane porous resin by a microporous film forming method using a laminating method, a polyurethane microporous film forming method using a direct coating method, and an ultra high density fabric method. It is a method of coating on the surface of a fibrous structure.

The conventional moisture-permeable waterproof fabric by the direct coating method using the polyurethane is the cause of environmental pollution by using solvents harmful to the environment, such as DMF (dimethylformamide) and MEK (methyl ethyl ketone), recently The method of manufacturing dry porous permeable waterproof fabric by using acid-type polyurethane coating solution and drying in multiple stages and dry coating method using hydrophilic non-porous polyurethane have been developed, but as described above, the moisture permeability and waterproof properties of polyurethane polymer resin The fiber structure has a disadvantage in that water does not pass smoothly due to the hydrophilic property of the polyurethane, and may cause a problem that the dye of the fiber structure is discolored by the organic solvent using an organic solvent in the manufacturing process.

Therefore, a moisture-permeable waterproof fiber structure in which a nanofiber coating layer in which micropores are formed on a surface of a fiber structure using nanofibers without the above problems has been developed. In the method for forming a polyurethane resin thin film layer described in Korean Patent Publication No. 2007-0109001, a polyethylene-based nano nonwoven fabric having a lower melting point or softening point than a polyurethane nanononwoven fabric with a thickness of 10 to 30 µm on a base fiber is used. After lamination, a method of manufacturing a moisture-permeable waterproof fabric by laminating a polyurethane nano nonwoven fabric having a thickness of 10 to 30 μm thereon, and forming a layer of a thin film as compared to a method of manufacturing a moisture-repellent waterproof fabric using a conventional adhesive. However, when applied to polyester-based fibers, there is a disadvantage that the adhesion between the polyolefin-based and polyester-based is incompatible with the interfacial separation, and the adhesive force is reduced, and the process is complicated because it has to go through the process of electrospinning heterogeneous polymers There is a limit.

In addition, conventional moisture-permeable nanofiber nonwoven fabrics include using a separate adhesive for bonding with the underlying fibers or forming a polyolefin-based nanofiber nonwoven fabric having a lower melting point or softening point than polyurethane nanofibers. The method of laminating to the base fiber by using a separate adhesive has a disadvantage in that the moisture permeability decreases and the overall fiber layer becomes thick.However, the method of forming the polyolefin-based nano nonwoven fabric has excellent moisture permeability, but it has to undergo two electrospinning processes. Due to the low compatibility between the polyolefin-based and polyester-based fabrics, there is a disadvantage in that the adhesive strength is weak due to the interface separation phenomenon.

 The present invention is to solve the above problems, the present invention is to form a nanofiber coating layer by laminating the nanofiber directly on the surface of the fiber structure without using a separate adhesive or heterogeneous polymer between the nanofiber layer and the fiber structure An object of the present invention is to provide a moisture-permeable waterproof fiber structure coated with nanofibers having excellent adhesive performance and a method of manufacturing the same.

In addition, the present invention by applying the step of laminating the nanofibers on the surface of the fiber structure by adding an ultraviolet curable photoinitiator to the polymer resin spinning solution, and then irradiating with ultraviolet rays to bond the process is simple and excellent adhesion of nanofibers waterproof moisture-proof coating It is an object to provide a method for producing a fibrous structure.

The present invention forms a nanofiber coating layer by electrospinning a polymer spinning solution to which the photoinitiator is added to the surface of the fiber structure, the nanofiber coating layer is bonded to the fiber structure by ultraviolet irradiation, characterized in that the nanofiber is coated Provide a waterproof fiber structure.

In addition, the photoinitiator is formed by mixing 1-hydroxycyclohexylphenyl ketone (Siga Co., Igacure 184) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in 9: 1 to 1: 9. It provides a moisture-permeable waterproof fiber structure coated with nanofibers.

In addition, the photoinitiator provides a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that 0.1 to 10% by weight compared to the polymer spinning solution.

In addition, the nanofiber coating layer provides a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that the thickness of 10 to 30㎛.

In addition, the moisture-permeable waterproof fiber structure coated with the nanofibers has a moisture-permeable moisture of 10,000g / ㎡ / 24hr (34 ℃, humidity 90%) and the water resistance is 5,000mmH ₂ O or more, characterized in that the waterproof moisture-proof coated nanofibers It provides a fibrous structure.

In addition, the present invention is a method for producing a water-permeable waterproof fiber structure, the mixing step of adding a photoinitiator to the polymer spinning solution; A coating layer forming step of forming a nanofiber coating layer by electrospinning a polymer spinning solution to which a photoinitiator is added to the surface of the fiber structure; It provides a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers, comprising the step of bonding the nanofiber coating layer and the fiber structure by irradiating the nanofiber coating layer with ultraviolet light.

In addition, the photoinitiator is formed by mixing 1-hydroxycyclohexylphenyl ketone (Siga Co., Igacure 184) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in 9: 1 to 1: 9. It provides a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers.

In addition, the nanofiber coating layer provides a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that the coating to a thickness of 10 to 30㎛.

In addition, the ultraviolet ray provides a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that irradiated with 0.6 to 10J / ㎠.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that in the drawings, the same components or parts denote the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

1 is a conceptual diagram showing an embodiment of the apparatus for producing a moisture-permeable waterproof fiber structure of the present invention, Figure 2 is an electrophotograph showing a cross-section of the moisture-permeable waterproof fiber structure produced by the embodiment of the present invention, Figure 3 is the present invention It is an enlarged electrophotographic nanofiber coating layer of the moisture-permeable waterproof fiber structure prepared in Examples.

The moisture-permeable waterproof fiber structure coated with nanofibers according to the present invention is prepared by forming a coating layer on the surface of the fiber structure as shown in FIG. 2 and electrospinning the polymer spinning solution in which the photoinitiator is added to the surface of the fiber structure. To form a nanofiber coating layer, the nanofiber coating layer is bonded to the fiber structure by ultraviolet irradiation.

The fibrous structure may be any flat fabric composed of fibers such as woven fabrics, knitted fabrics, felts, plates, nonwoven fabrics, adhesive fabrics, mold fabrics, webs, etc., which are manufactured by mixing natural fibers or synthetic fibers alone or in combination. It may be desirable to use a nonwoven fabric with the best adhesion to the fiber coating layer.

The nanofiber coating layer is coated on the fiber structure in the form of a nanofiber nonwoven fabric to form a myriad of fine pores between the nanofibers as shown in FIG. 3 to provide moisture permeability and waterproofness to the fiber structure.

The photoinitiator refers to a substance that starts the polymerization reaction by absorbing energy such as ultraviolet rays. There are various types such as a single cleavage free radical photoinitiator and a hydrogen suction type free radical photoinitiator, and one of them can be selectively used, but the characteristics of each photoinitiator It would be desirable to mix and use according to

In the present invention, 1-hydroxycyclohexylphenyl ketone (Igacure 184, Ciba) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) is prepared by mixing 9: 1 to 1: 9 Would be desirable.

The photoinitiator mixed with the 1-hydroxycyclohexylphenyl ketone and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide not only allows sufficient curing at the surface but also diphenyl 2,4,6-trimethyl By using benzoyl phosphine oxide it is possible to cure deep to the inside there is an advantage that can be sufficiently cured even a thick coating layer.

In addition, the photoinitiator is preferably added 1 to 10% by weight, more preferably 1 to 6% by weight compared to the polymer spinning solution.

When the content of the photoinitiator exceeds 10% by weight, the radioactivity of the nanofibers is significantly worsened during electrospinning, which makes the electrospinning itself difficult, as well as the surface hardening during ultraviolet irradiation even when the nanofibers are radiated to form a nanofiber coating layer. Since the adhesive force to the fiber structure is not cured until the inside of the coating layer is lowered and the content of the photoinitiator is less than 0.1% by weight, the curing effect due to ultraviolet irradiation is insignificant and the adhesive force to the fiber structure is reduced.

The nanofiber coating layer is preferably coated on the surface of the fiber structure to a thickness of 10 to 30㎛. If the nanofiber coating layer is less than 10㎛ moisture permeability is good but the waterproofness may fall, if the nanofiber coating layer exceeds 30㎛ water resistance is good but the moisture permeability may be inferior.

The manufacturing method of the water-permeable waterproof fiber structure coated with nanofibers according to the present invention as described above is prepared by mixing, forming a coating layer, bonding step.

In the mixing step, a photoinitiator is added to the polymer spinning solution, and 0.1 to 10% by weight of the photoinitiator is added to the polymer spinning solution to prepare the polymer spinning solution to which the photoinitiator is added.

The photoinitiator is prepared by mixing 1-hydroxycyclohexylphenyl ketone (Igacure 184, Ciba) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in 9: 1 to 1: 9. Would be desirable.

Forming a nanofiber coating layer on the surface of the fiber structure by electrospinning the polymer spinning solution to which the photoinitiator is added, the nanofiber coating layer forms a coating layer in the same manner as the nonwoven fabric manufacturing method. The nanofiber coating layer is preferably coated with a thickness of 10 to 30㎛.

The nanofiber coating layer coated on the fiber structure is a bonding step of firmly bonding the nanofiber coating layer to the fiber structure by irradiating ultraviolet light of 0.6 to 10J / cm 2 and the nanofiber coating layer is bonded to the fiber structure by curing the ultraviolet light. The microporous is controlled in the nanofiber coating layer to prepare a moisture-permeable waterproof fiber structure coated with the nanofiber of the present invention.

The electrospinning method of the nanofibers in the coating step is irrelevant to any one of the conventional electrospinning method using only electric force, air supply electrospinning method, and air chamber electrospinning method having an air chamber, but it has excellent uniformity of nanofibers. Coating with an air chamber electrospinning method to produce a nonwoven fabric may produce a moisture-permeable waterproof fiber structure coated with a uniform nanofiber of the nanofiber coating layer.

An air chamber electrospinning method for manufacturing a nanofiber-coated moisture-permeable fiber structure of the present invention as shown in Figure 1 spinneret pack 100, stream induction unit 200, the first concentrator 300, A manufacturing apparatus consisting of the nanofiber induction part 400, the air chamber 500, the laminator 600, the second concentrator 700, and the calendar part 800 may be used.

In the manufacturing apparatus configured as described above, the spinneret pack 100 is composed of a plurality of spinning nozzles. The spinneret is a device for discharging nanofibers by electrospinning a polymer spinning solution to which a photoinitiator supplied from a spinning solution supply unit is electrospun through a nozzle. A uniform spinning solution is supplied to each spinning nozzle of the pack 100 at a uniform pressure to spin and discharge the nanofibers by the voltage applied to the spinneret pack 100.

Since the nanofibers emitted from the spinneret pack 100 are discharged without direction, a stream induction part 200 is formed at the bottom of the spinneret tag 100 so that the discharged nanofibers are directed to a predetermined place, and the nanofibers induced by the stream induction part 200 are reticulated. It is distributed and focused on the first concentrator of the structure.

The nanofibers focused on the first concentrator are guided to the nanofiber guide unit 400 which guides and transports the nanofibers to the through-holes of the network structure by the downdraft before being laminated and bonded. The downdraft is generated in the airflow generation unit installed in the nanofiber induction unit 400, and the downdraft generated in the airflow generation unit 410 lowers the nanofibers focused on the first concentrator to guide the nanofiber induction unit 400. Transfer to air chamber 500.

The air chamber 500 has a transport path 510 in the form of a normal light down strait, and the nanofibers passing through the transport path are gradually attenuated and elongated by the transport path 510 and the downdraft which become narrower as they descend. While descending along the airflow.

The nanofibers transferred through the transport path 510 of the air chamber are discharged through the stacker 600 formed at the end of the air chamber and integrated in the second concentrator 700.

The fiber structure is placed in the second concentrator so that the surface structure of the fiber structure nanofibers is formed of a nonwoven fabric coating layer.

In addition, an exhaust unit 900 capable of discharging downdrafts generated by the airflow generator 410 may be formed at a lower end of the second concentrator 700.

According to the present invention, the nanofiber coating layer bonds the fiber structure to the fiber structure by curing the nanofiber coating layer by UV irradiation, and adjusts the micropores of the nanofiber by UV irradiation to control the fiber structure having an ultra-thin coating layer having excellent moisture permeability and water resistance. There is an effect to manufacture.

In addition, by forming a coating layer of nanofibers prepared by electrospinning a polymer spinning solution to which a photoinitiator is added without using an adhesive or a heterogeneous polymer, the process is simplified and thus advantageous in mass production.

The fiber structure of the nanofiber coating layer of the present invention prepared as described above can be used not only as a high performance filter material, various packaging materials, but also useful in all industries such as various wipers, medical and clothing.

Hereinafter, the present invention will be described in detail through examples. However, the present invention is not limited to the following examples.

Example

A solution was prepared by dissolving a polyurethane resin having a number average molecular weight of 90,000 in N, N-dimethylformamide at 8% by weight, and then preparing 1-hydroxy cyclohexyl phenylketone (Sivasa, Igacure 184) and di A spin solution was prepared by adding 3 wt% of a photoinitiator mixed with phenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in a 4: 1 ratio to a polyurethane solution. The prepared spinning solution was measured using a rheometer (Rheometer DV, Brookfield Co., USA) and the viscosity measured was 530 centipoas (cps). The conductivity is also 0.279 mS / m, as measured by a conductor meter (CM-40G, TOA electronics Co., Japan).

The polymer spinning solution to which the photoinitiator is prepared is added using the spinning apparatus shown in FIG. 1.

The number of spinning nozzles in the spinneret is 480 holes, the applied voltage is 25kV, the spinning distance is 20 cm, the air speed is 8 m / sec, and the reciprocating movement of the focusing device is 30 times / min. A nanofiber corti layer having a fiber diameter of 400 to 500 nm was formed and a thickness of the corti layer was prepared at 25 μm.

The fibrous structure used a nonwoven fabric made of polyester.

The nanofiber-coated fiber structure prepared by the above method was UV-cured by irradiation energy of 4.0 J / cm 2 using a metal halide lamp to prepare a moisture-permeable waterproof fiber structure.

Comparative example

Prepared in the same manner as in Example 1 except that a polyurethane resin having a number average molecular weight of 90,000 was dissolved in N, N-dimethylformamide at 8% by weight to prepare a solution, and then spun without adding a photoinitiator to have a fiber diameter of 200 to 300 nm. To form a nanofiber coating layer and the thickness of the corty layer was prepared a waterproof breathable fiber structure of 25㎛.

* The moisture-permeable waterproof fiber structure manufactured through the above Examples and Comparative Examples was washed at 41 ° C. with AATCC Test Method 135-1995 and dried by a tumble drying method, followed by ASTM E96 (CaCl 2) method at 34 ° C., humidity 90%, 24%. Moisture permeability was evaluated over time, and the water resistance was measured at an ascending rate of 600 mm / min by ISO 0811 and the results are shown in Table 1.

division Coating layer thickness (㎛) Permeability (g / ㎡ / 24hr) Hydraulic pressure (mmH ₂ O) Example 25 10,500 6,000 Comparative example 25 6,500 3,000

As shown in the results of Table 1, the moisture-permeable waterproof fiber structure of the embodiment coated with the moisture-permeable waterproof coating according to the present invention can be seen that the moisture permeability and the water resistance are nearly twice higher than the fiber structure of the comparative example.

Therefore, the moisture-permeable waterproof fiber structure prepared by the manufacturing method of the present invention is the water vapor transmission rate of 10,000 g / ㎡ / 24hr or more evaluated at 34 ℃, 90% humidity by 24 hours by ASTM E96 (CaCl2) method, according to ISO 0811 It can be seen that the water pressure measured at the rising speed of 600 mm / min is 5,000 mmH 2 O or more.

1 is a conceptual view showing an embodiment of the apparatus for producing a moisture-permeable waterproof fiber structure of the present invention.

Figure 2 is an electrophotograph showing a cross section of the moisture-permeable waterproof fiber structure produced by the embodiment of the present invention.

Figure 3 is an enlarged electrophotographic nanofiber coating layer of the moisture-permeable waterproof fiber structure prepared in the embodiment of the present invention.

<Code Description of Main Parts of Drawing>

100: spinneret pack 110: spinning liquid supply device

200: stream guide unit 300: first focusing device

400: nanofiber induction part 500: air chamber

600: stacker 700: second focusing machine

800: calendar unit 900: exhaust unit

Claims (9)

A nanofiber coating layer is formed by electrospinning a polymer spinning solution containing a photoinitiator on the surface of the fiber structure, The nanofiber coating layer is moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that bonded to the fiber structure by ultraviolet irradiation. The method of claim 1, The photoinitiator is formed by mixing 1-hydroxycyclohexylphenyl ketone (Igacure 184, Ciba, Inc.) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in 9: 1 to 1: 9. Nanofiber-coated moisture-permeable fiber structure characterized in that the coating. The method of claim 1, The photoinitiator is a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that added 0.1 to 10% by weight compared to the polymer spinning solution. The method of claim 1, The nanofiber coating layer is a moisture-resistant waterproof fiber structure coated with nanofibers, characterized in that the thickness of 10 to 30㎛. The method of claim 1, The moisture-permeable waterproof fiber structure coated with the nanofibers has a moisture-permeability of 10,000 g / m 2 / 24hr (34 ° C., a humidity of 90%) and a water resistant pressure of 5,000 mmH ₂ O or more, wherein the moisture-permeable waterproof fiber structure is coated with nanofibers. . In the manufacturing method of the moisture-permeable waterproof fiber structure, Adding a photoinitiator to the polymer spinning solution; A coating layer forming step of forming a nanofiber coating layer by electrospinning a polymer spinning solution to which a photoinitiator is added to the surface of the fiber structure; Method of manufacturing a water-permeable waterproof fiber structure coated with nanofibers, comprising the step of bonding the nanofiber coating layer and the fiber structure by irradiating the nanofiber coating layer with ultraviolet light. The method of claim 6, The photoinitiator is formed by mixing 1-hydroxycyclohexylphenyl ketone (Igacure 184, Ciba, Inc.) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Darocur TPO) in 9: 1 to 1: 9. Method for producing a moisture-permeable waterproof fiber structure coated with nanofibers. The method of claim 6, The nanofiber coating layer is a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that the coating to a thickness of 10 to 30㎛. The method of claim 6, The ultraviolet ray is a method for producing a moisture-permeable waterproof fiber structure coated with nanofibers, characterized in that irradiated with 0.6 to 10J / ㎠.

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