KR20090124293A - Moisture permeable and water proof web using nano fiber and fabrication method thereof - Google Patents

Abstract

PURPOSE: Moisture permeable and water proof web using nano-fiber and a manufacturing method thereof are provided to offer hydrophilic and hydrophobic polymers, and to improve permeability of the nano-fiber. CONSTITUTION: Moisture permeable and water proof web includes at least one or more hydrophilic polymer fiber layer(100) and one or more hydrophobic polymer fiber layer(101). The average diameter of the hydrophilic polymer fiber layer is 50 ~ 3,000 nm. The hydrophobic polymer fiber layer has the average diameter of 50 ~ 3,000 nm. The whole thickness of the web is 3 ~ 20 μm. The porosity of the web is 50 ~ 90%. A plurality of pores having the diameter of 0.5 ~ 3 μm are formed on the moisture permeable and water proof web.

Description

Moisture permeable and water proof web using nano fiber and fabrication method

The present invention relates to a functional web, and more particularly, to a moisture-permeable waterproof web using a nanofiber having a structure capable of providing both hydrophilicity and hydrophobicity, and a manufacturing method thereof.

The moisture-permeable waterproof material blocks the penetration of external moisture such as fog, rain and snow, and permeates fine moisture such as sweat, and so on. Mountaineering items such as mountaineering clothes, sleeping bags, hats and gloves, outdoor clothing, training clothes and ski clothes. It is widely applied to various apparel products requiring moisture permeability and breathability, such as sports goods such as golf wear.

Water-permeable waterproof materials are usually used in the form of films and coatings. Products in the form of coatings are usually formed of urethanes and used as general purpose products, and products in the form of films are used as high performance and expensive products having a non-porous or porous structure. Porous films are more suitable for applications requiring high moisture permeability, but it is true that such film products also have many difficulties in achieving high porosity and small pore size.

Fabrics with moisture-permeable waterproofing are largely classified into laminating type products, dry type products and wet type products according to manufacturing technology. The laminating method product is a moisture-permeable waterproof fabric is manufactured by bonding a separately prepared moisture-permeable film to a fabric, and the dry and wet anti-corrosive products are manufactured by directly coating a resin to be a moisture-permeable film on the fabric.

Regarding the manufacture of a moisture-permeable waterproof fabric, Korean Patent Laid-Open No. 2000-0016623 relates to an absorbent product in which a hydrophobic polymer is coated with a hydrophilic material to impart wettability to water or an aqueous solution, thereby lowering the surface tension of water to increase absorption. Techniques are disclosed.

Korean Patent Publication No. 2002-0060876 discloses a dry, non-porous moisture-permeable fabric manufactured by manufacturing a hydrophobic fabric by dry coating and then bonding a hydrophilic resin layer using an adhesive again. In this patent, the moisture-permeable waterproof film is a porous film membrane prepared by coating a resin, not a fiber.

In Korean Patent Publication No. 2006-0022406, in the manufacture of a nanofiber nonwoven fabric by electrospinning on a collector through a spinning nozzle while supplying a high voltage to a spinning solution which is a polymer resin solution, a water- and oil-repellent agent is added to and mixed with the spinning solution. Disclosed is a method of manufacturing a nanofiber nonwoven fabric, characterized in that. This patent proposes a technique for producing a nanofiber nonwoven fabric provided with moisture permeability and waterproof performance by mixing a water repellent agent and an oil repellent agent as an spinning solution and then electrospinning the mixture solution.

In addition, the Republic of Korea Patent Registration No. 749965 discloses a fabric made of polyvinylidene difluoride (PVDF) nanofibers excellent in water repellency and moisture-permeable waterproof. In this patent, nanofiber has good moisture permeability and water resistance, but the hydrophobic PVDF polymer alone is composed of a fabric, which limits its ability to absorb and dissipate moisture.

As described above, the conventional patents disclose techniques for forming a moisture-permeable waterproof fabric as a single fiber layer or by coating a film or a resin that is not in the form of a fiber.

The present invention has been made to improve the prior art as described above, the hydrophilic polymer layer and the hydrophobic polymer layer is made of nanofibers, moisture permeability with the structure of the diameter of the nanofibers optimized to improve the water pressure and moisture permeability and breathability It is an object of the present invention to provide a waterproof web and a method of manufacturing the same.

Another object of the present invention is to provide a water-permeable waterproof web and a method of manufacturing the same having a structure in which the thickness, pores, etc. of the nanofiber web are optimized for improving water pressure, moisture permeability, and breathability.

The present invention to achieve the above object is at least one layer of hydrophilic polymer fiber layer made of fibers having an average diameter of 50 ~ 3,000nm; And at least one hydrophobic polymer fiber layer bonded to the hydrophilic polymer fiber layer and composed of fibers having an average diameter of 50 to 3,000 nm.

The total thickness of the moisture-permeable waterproof web is preferably 3 to 20 μm.

In addition, the porosity (porosity) of the moisture-permeable waterproof web is preferably 50 to 90%.

The water-permeable waterproof web is preferably formed with a plurality of pores having a size of 0.5 ~ 3㎛ diameter.

According to another aspect of the invention, the step of forming at least one layer of the first fibrous layer using a hydrophilic polymer solution (or hydrophobic polymer solution); And forming at least one second fiber layer bonded to the first fiber layer by using a hydrophobic polymer solution (or a hydrophilic polymer solution), wherein the first fiber has an average diameter of 50 to 3,000 nm. Provided is a method for producing a moisture-permeable waterproof web, wherein the fiber layer and the second fiber layer are formed.

The first fiber layer and the second fiber layer is preferably formed so that the total thickness of the web is 3 ~ 20㎛.

In addition, the first fiber layer and the second fiber layer is preferably formed so that a plurality of pores having a size of 0.5 ~ 3㎛ diameter formed in the web.

As a process for bonding the first fiber layer and the second fiber layer, any one or two or more selected from an electrospinning method, an ultrasonic bonding method, a thermal fusion method, a compression method, and a bonding method by an adhesive may be adopted.

According to the present invention, the moisture-permeable waterproof web composed of a hydrophilic high molecular fiber layer and a hydrophobic polymer fiber layer made of nanofibers having an average diameter of 50 to 3,000 nm has excellent breathability when applied to clothing, and quickly absorbs sweat emitted from the skin from the hydrophilic polymer fiber layer. By discharging to the outside through the capillary phenomenon, it is possible to maintain the comfort of the skin by blocking the penetration of external moisture such as fog, rain, snow in the hydrophobic polymer fiber layer.

In addition, the moisture-permeable waterproof web according to the present invention has both hydrophilic polymer layer and hydrophobic polymer layer composed of nanofiber layers, so that it is possible to improve the water pressure and moisture permeability characteristics compared to the conventional film or resin coated web, and it is light in weight and has excellent breathability. There is this.

In addition, the moisture-permeable waterproof web according to the present invention can be usefully applied as work clothes in a clean room because it has excellent microparticle control ability, and can be applied to various industrial fields such as uses for protecting the human body from toxic biological / chemical substances.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

1 to 4 are cross-sectional views showing the configuration of the water-permeable waterproof web according to the embodiments of the present invention.

1 to 4, the moisture-permeable waterproof web has a structure in which at least one hydrophilic polymer fiber layer 100 and at least one hydrophobic polymer fiber layer 101 are combined.

Specifically, FIG. 1 illustrates a structure in which a hydrophobic polymer fiber layer 101 is stacked on a hydrophilic polymer fiber layer 100, and FIG. 2 illustrates a structure in which a hydrophilic polymer fiber layer 100 is stacked between a hydrophobic polymer fiber layer 101. 3 shows a structure in which a hydrophobic polymer fiber layer 101 is stacked between the hydrophilic polymer fiber layers 100. In addition, the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 are alternately stacked in FIG. 4, and the hydrophilic polymer fiber layer 100 ′ and the hydrophobic polymer fiber layer 101 ′ having a heterogeneous composition are stacked. have.

The hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 constituting the moisture-permeable waterproof web are composed of nanofibers having an average diameter of 50 to 3,000 nm. Nanofibers having such a numerical range have numerous pores having a diameter of 0.5 to 3 μm in the water vapor barrier web. Therefore, the moisture-permeable waterproof web including the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 passes water vapor or moisture having a diameter of 0.0004 μm generated in the human body, and a fog having a diameter of 50 to 600 μm generated in a natural state. Water particles such as raindrops are blocked to provide both moisture permeability and water resistance.

In view of the moisture-permeable waterproof performance, the porosity of the web formed by the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 is preferably 50 to 90%.

Polymeric materials used as the raw material of the fibers forming the moisture-permeable waterproof web include polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyvinylidene chloride-acrylonitrile copolymer, and polyethylene oxide. , Polyurethane, polymethylacrylate, polymethylmethacrylate, polyacrylamide, polyvinylchloride, polyvinylacetate, polyvinylpyrrolidone, polytetraethylene glycol diacrylate, polyethyleneglycol dimethacrylate, cellulose, Natural or synthetic high molecular materials such as cellulose acetate, rayon, polyamide, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, polyvinyl alcohol, polysulfone and polyisulfone Can be adopted have. In addition, the polymer may be used by partially or both modifying a hydrophilic group such as a carboxyl group, a hydroxyl group, a hydroxyl group, an amino hydrophilic group and a chain hydrocarbon group, an aromatic hydrocarbon group, an halogenated alkyl group, an organosilicon group, and a fluorine group.

Preferably, in the present invention, the criterion of 'hydrophobicity' is defined as a case where the process water content is 2.5% or less in the KS K0301 standard, and the 'hydrophilicity' has a process water content difference of 0.5% or more (preferably 1% or more difference) with hydrophobicity. May be defined as).

The thickness of the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 is determined by the stacking amount of fibers. Preferably, the overall thickness range of the web is determined to be 1 to 100 µm, more preferably 3 to 20 µm in consideration of the moisture permeability and the water pressure resistance characteristics of the moisture-permeable waterproof web. In the present invention, by manufacturing a web using nanofibers having an average diameter of 50 to 3,000 nm, it is possible to satisfy both pore conditions of 0.5 to 3 μm in diameter and thickness range of 3 to 20 μm.

The water vapor permeability among the characteristics of the water-permeable waterproof web is expressed in weight (mg) the amount of water vapor passing per unit area (m 2) for 24 hours, and the water pressure is expressed in height (mm) that can withstand water without permeating water. will be. Generally, the moisture permeability is classified into high moisture permeability of more than 6,000 (g / ㎡), and the water resistance is low water resistance type (300 ~ 800mm / H ₂ O), medium water resistance type (1,000 ~ 2,500mm / H ₂ O), high water resistance Molds (5,000 to 30,000 mm / H ₂ O).

Electrospinning may be preferably used as a method of bonding the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 to each other in order to manufacture a moisture-permeable waterproof web. In addition, ultrasonic bonding, heat fusion, compression, and adhesive Various methods such as the joining method can be adopted.

Hereinafter, the moisture permeability and water resistance characteristics according to the number and thickness of the hydrophilic polymer fiber layer 100 and the hydrophobic polymer fiber layer 101 constituting the moisture-permeable waterproof web will be described through Examples 1 to 8. Here, the moisture permeability characteristics were evaluated according to the KS K0594 standard, and the water pressure resistance characteristic was evaluated according to the KS K0591 standard.

Example  1 to 2

CYTEC's UCECOAT AB7300, a hydrophilic polymer material, was diluted in a solvent to prepare a 16% (wt / wt) hydrophilic solution, and PELLETHANE, a hydrophobic polymer material, was dissolved in a solvent to prepare a 16% (wt / wt) hydrophobic solution. .

Then, by supplying a high voltage of 55kV to the hydrophilic solution and the hydrophobic solution was electrospun to prepare a moisture-permeable waterproof web having a hydrophilic polymer fiber layer 100 and a hydrophobic polymer fiber layer 101.

Electrospinning formed a hydrophilic polymer fiber layer 100 by spinning a hydrophilic polymer of a predetermined thickness on a collector (collector) to form a hydrophilic polymer fiber layer 100, and by spinning again by spinning a hydrophobic polymer of a predetermined thickness on the hydrophobic polymer fiber layer 101, At this time, the sum of the thicknesses of the polymer fiber layer and the hydrophobic polymer fiber layer 101 was set to 20 μm.

After all electrospinning processes were completed, the prepared moisture-permeable waterproof web was dried at a temperature of 50 ° C.

Example  3 to 4

A 16% (wt / wt) hydrophilic solution was prepared by diluting CYTEC's UCECOAT AB7300 hydrophilic polymer material in a solvent, and a 16% (wt / wt) hydrophobic solution was prepared by dissolving ARKEMA's KYNAR761 in a solvent. Other manufacturing process conditions were the same as in Examples 1 and 2.

Example  5 to 8

As a hydrophilic polymer material, CYTEC's UCECOAT AB7300 was diluted in a solvent to prepare a 16% (wt / wt) solution, and as a hydrophobic polymer, DOW CHEMICAL's PELLETHANE was dissolved in a solvent to prepare a 16% (wt / wt) solution. Process conditions except the number of repetitions of the fiber layer and the thickness of the layer were the same as in Examples 1 and 2.

Referring to Table 1, which summarizes the evaluation results, the moisture-permeable waterproof webs of Examples 1 to 8 exhibit high moisture-permeability characteristics with a moisture permeability of more than 15,000 g / m 2 / day and a water pressure of 6,000 mmH ₂ O. It can be confirmed that the characteristics of the high pressure resistance type exceed all of them.

Hereinafter, a method of manufacturing a moisture-permeable waterproof web using an electrospinning method according to a preferred embodiment of the present invention will be described.

Apparatus for performing the electrospinning method includes a solution pump for supplying a polymer solution, a spinning unit having a single or multiple spinning nozzles, a high voltage generator for supplying a high voltage for electrospinning the polymer solution, electrospinning Known electrospinning apparatus including a collector for collecting nanofibers can be used. The electrospinning apparatus is disclosed in Korean Patent Registration Nos. 436602 and 458946, which are filed by the present applicant, and the detailed description thereof will be omitted.

First, when the electrospinning is performed by applying a high voltage to the spinning nozzle and the collector while supplying a hydrophilic polymer solution to the spinning nozzle using a solution pump, the first fiber layer corresponding to the hydrophilic polymer fiber layer 100 is integrated with the nanofibers. Is formed.

After forming the first fibrous layer, before the solvent of the first fibrous layer is completely dried, it is electrospun while supplying a hydrophobic polymer solution using a solution pump to form a second fibrous layer corresponding to the hydrophobic polymer fiber layer 101 on the first fibrous layer. As a result, a moisture-permeable water-proof web in which hydrophilic and hydrophobic fiber layers are laminated is manufactured. Here, when the second fiber layer is formed before the solvent of the first fiber layer is completely dried, the solvent of the first fiber layer and the second fiber layer is evaporated at the same time, so that the bonding action proceeds between the hydrophilic polymer and the hydrophobic polymer fiber to form a substantially integral web. Therefore, no separate bonding process is required.

In performing the electrospinning method as described above, the spinning nozzle preferably has a specification capable of discharging the solution such that the average diameter of the nanofibers forming the hydrophilic polymer fiber layer 100 is 50 to 3,000 nm. In addition, it is preferable that the discharge amount of the spinning nozzle and the conveying speed of the collector are set so that the sum of the thicknesses of the first fiber layer and the second fiber layer is 3 to 20 µm.

The first fibrous layer and the second fibrous layer may be repeatedly formed according to the required number of fibrous layers.

Although the present invention has been described above by means of limited embodiments and drawings, the present invention is not limited thereto and will be described below by the person skilled in the art to which the present invention pertains. Of course, various modifications and variations are possible within the scope of the claims.

The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the detailed description of the present invention serve to further understand the technical spirit of the present invention, the present invention includes matters described in such drawings. It should not be construed as limited to.

1 is a cross-sectional view of a moisture-permeable waterproof web having a structure in which a hydrophobic polymer fiber layer is stacked on a hydrophilic polymer fiber layer according to an embodiment of the present invention.

2 is a cross-sectional view of a moisture-permeable waterproof web having a structure in which a hydrophilic polymer fiber layer is stacked between hydrophobic polymer fiber layers according to another embodiment of the present invention.

3 is a cross-sectional view of a moisture-permeable waterproof web having a structure in which a hydrophobic polymer fiber layer is stacked between hydrophilic polymer fiber layers according to another embodiment of the present invention.

4 is a cross-sectional view of a moisture-permeable waterproof web having a structure in which a hydrophilic polymer fiber layer and a hydrophobic polymer fiber layer are alternately stacked according to another embodiment of the present invention.

<Description of Major Reference Marks in Drawings>

100,100 ': hydrophilic polymer fiber layer 101,101': hydrophobic polymer fiber layer

Claims (8)

At least one hydrophilic polymer fiber layer composed of fibers having an average diameter of 50 to 3,000 nm; And And at least one hydrophobic polymer fiber layer bonded to the hydrophilic polymer fiber layer and composed of fibers having an average diameter of 50 to 3,000 nm. The method of claim 1, Water-permeable waterproof web, characterized in that the total thickness of the web is 3 ~ 20㎛. The method according to claim 1 or 2, Water-permeable waterproof web, characterized in that the porosity (porosity) of the web is 50 to 90%. The method according to claim 1 or 2, Water-permeable waterproof web, characterized in that a plurality of pores are formed having a diameter of 0.5 ~ 3㎛. Forming at least one first fibrous layer using a hydrophilic polymer solution (or hydrophobic polymer solution); And And forming at least one second fiber layer bonded to the first fiber layer by using a hydrophobic polymer solution (or a hydrophilic polymer solution). Forming the first fiber layer and the second fiber layer so that the average diameter of the fiber is 50 ~ 3,000nm. The method of claim 5, Forming the first fiber layer and the second fiber layer so that the overall thickness of the web is 3 ~ 20㎛. The method according to claim 5 or 6, Method for producing a water-permeable waterproof web, characterized in that for forming a plurality of pores having a size of 0.5 ~ 3㎛ diameter on the web and the first fiber layer and the second fiber layer. The method of claim 5, Preparation of a moisture-permeable waterproof web characterized in that any one or two or more processes selected from the electrospinning method, ultrasonic bonding method, thermal fusion method, bonding method and bonding method by bonding to bond the first fiber layer and the second fiber layer. Way.

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