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WO2013066022A1 - Film de nanofibres stratifiés et procédés pour sa production et composite de nanofibres les utilisant - Google Patents

Film de nanofibres stratifiés et procédés pour sa production et composite de nanofibres les utilisant Download PDF

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Publication number
WO2013066022A1
WO2013066022A1 PCT/KR2012/008983 KR2012008983W WO2013066022A1 WO 2013066022 A1 WO2013066022 A1 WO 2013066022A1 KR 2012008983 W KR2012008983 W KR 2012008983W WO 2013066022 A1 WO2013066022 A1 WO 2013066022A1
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Prior art keywords
polymer
melting point
nanofiber web
low
spinning
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English (en)
Korean (ko)
Inventor
김경수
김찬
서인용
이승훈
정용식
김윤혜
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Amotech Co Ltd
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Amotech Co Ltd
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • the present invention relates to a laminated nanofiber web having a coating effect on its surface for improving the durability of the nanofiber web, a method of manufacturing the same, and a nanofiber composite material using the same, specifically, obtained by electrospinning two or more polymers.
  • the present invention relates to a laminated nanofiber web and a method of manufacturing the same, and a nanofiber composite material having a coating effect applied to a surface by preparing a laminated nanofiber web of two or more layers and partially melting the surface layer of the nanofiber web through a thermocompression bonding process.
  • Conventional waterproofing is to coat or laminate the rubber or acrylic resin to prevent rain or water from penetrating from the outside to have a fully waterproof function.
  • it does not emit sweat, steam, heat, etc. from the inside, so that the problem of unpleasant feelings arises when worn, and the material which appeared to solve this problem is a moisture-permeable waterproof material.
  • Moisture-permeable waterproof material blocks moisture from the outside such as fog, rain and snow, and permeates fine moisture such as sweat, and so on climbing products such as hiking clothes, sleeping bags, hats, gloves, sportswear, military uniforms, tents, etc. It is a widely used fabric that can be encountered frequently in life.
  • the electrospinning method is a technique for obtaining nanofibers having a three-dimensional laminated structure simultaneously with spinning by an electric field formed by applying a high voltage to the polymer melt, it is possible to control the size of the pores by controlling the fiber diameter, lamination.
  • the electrospinning nanoweb has a disadvantage in that the mechanical properties are significantly lower than the conventional film-type membranes, and since the nanofibers are not bonded and fixed, mechanical properties such as strength are significantly lower than those of conventional materials. There is a disadvantage that peeling or scratching occurs.
  • Korean Patent Application Publication No. 10-2011-0095753 proposed by the present applicant provides a blend of electrospun polymers having different melting points or a nanofiber web through cross-electrospinning, and partially melts a low melting polymer material to provide mechanical properties. It is disclosed a method of manufacturing a nanofiber composite by preparing a self-sealing nanofiber web improved by bonding it to a fabric.
  • the low melting polymer and the high melting polymer nanofiber are distributed evenly throughout the web, so that partial melting may improve the bonding strength between the nanofibers constituting the web. Since it is difficult to uniformly control the pore distribution of the fibrous web, there is a limit in implementing high water pressure, and also the water resistance is drastically lowered due to the contamination problem caused by the penetration of detergent during washing.
  • the present invention is to solve the above problems, an object of the present invention is to produce a two-layer or multi-layer nanofiber web obtained by electrospinning two or more kinds of polymers having different melting points, the surface layer is thermally compressed It is to provide a nanofiber web and a method of manufacturing the same by partially melting through imparting a surface coating effect.
  • Another object of the present invention is to partially melt the surface of the nanofiber web through heat compression processing to impart a surface coating effect, thereby preventing surface scratches caused by external forces and water resistance deterioration due to infiltration of detergent during washing. It is to provide a nanofiber web with a function of.
  • Still another object of the present invention is to provide a composite sheet composited with a base fabric provided with a waterproof function to the nanofiber web prepared above, or a breathable waterproof fiber structure having maximum breathability, moisture permeability, and softness.
  • Still another object of the present invention is to provide a composite sheet having functionality such as washing durability, scratch durability, etc., in the composite sheet provided with water pressure resistance, moisture permeability, and breathability.
  • a nanofiber layer of a high melting point polymer and a nanofibrous layer of a low melting point polymer formed on the nanofibrous layer of the high melting point polymer, wherein the nanofibers of the low melting point polymer are partially melted to provide a laminated nanofiber web.
  • the base material Nanofibrous layers of high melting point polymers formed on one or both surfaces of the base material; And a nanofibrous layer of a low melting point polymer formed on the nanofibrous layer of the high melting point polymer, wherein the nanofibers of the low melting point polymer are partially melted to provide a laminated nanofiber composite.
  • the low-melting and high-melting polymers are low-polymer polyurethane (polyurethane), high-polymer polyurethane, PS (polystylene), PVA (polyvinylalchol), PMMA (polymethyl methacrylate), polylactic acid (PLA: polylactic acid), PEO (polyethyleneoxide) , PVAc (polyvinylacetate), PAA (polyacrylic acid), polycaprolactone (PCL: polycaprolactone), PAN (polyacrylonitrile), PVP (polyvinylpyrrolidone), PVC (polyvinylchloride), nylon (Nylon), PC (polycarbonate), PEI (polyetherimide) , PVdF (polyvinylidene fluoride), PES (polyesthersulphone) is characterized in that the manufacturing by selecting a polymer having a different melting point.
  • the solvent is DMAc (dimethyl acetamide), DMF (N, N-dimethylformamide), NMP (N-methyl-2-pyrrolidinone), DMSO (dimethyl sulfoxide), THF (tetra-hydrofuran), EC (ethylene carbonate), DEC (DEC) diethyl carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), water, acetic acid, formic acid, chloroform, chloroform, dichloromethane and acetone It is characterized in that any one or more selected from the group consisting of.
  • the polymer material is characterized in that mixed in 5 to 22.5% by weight in each spinning solution for electrospinning.
  • the solvent used in the spinning solution is characterized in that the two-component solvent mixed with a high boiling point (BP: boiling point) and low.
  • the low melting point polymer has a melting point of 50 to 170 ° C, and the high melting point polymer has a melting point of 80 to 250 ° C.
  • the base material is characterized in that any one or more selected from woven paper, nonwoven fabric, foam, paper, mesh.
  • the nanofiber web is composed of multiple layers of two or more layers.
  • the base material may be formed in a two-layer structure with the nanofiber web, or may be formed in a three-layer structure in which the nanofiber web is interposed between the base material.
  • the low-melting-point nanofibers are partially melted in the thermocompression process of the nanofiber web obtained by electrospinning polymer materials having different melting points, thereby improving the fastness of external scratches, washing durability, and the like. It can be usefully applied in the manufacture of lightweight materials having excellent moisture permeability, water resistance and thermal insulation can be adjusted in various ways.
  • FIG. 1 is a schematic diagram of air electrospinning for schematically illustrating a process of manufacturing a nanofiber web according to the present invention
  • FIG. 2 is a manufacturing process diagram for schematically illustrating a process of manufacturing a nanofiber composite according to the present invention
  • Example 6 is a scanning electron micrograph of a nanofiber web prepared by Example 3 of the present invention.
  • Example 7 is a scanning electron micrograph of a nanofiber web prepared by Example 4 of the present invention.
  • Example 8 is a scanning electron micrograph of the nanofiber web prepared by Example 5 of the present invention.
  • the melting point of the low melting point and the high melting point polymer using a different solvent to prepare a first spinning solution and a second spinning solution and using different spinning nozzles
  • the obtained nanofiber web is subjected to a thermocompression process (eg, calendaring) to partially melt the nanofibers of a low melting polymer component. It is possible to produce a laminated nanofiber to give a surface coating effect.
  • the nanofiber web formed by electrospinning using low melting point and high melting point polymers is subjected to heat treatment such as calendering, the nanofibers of low melting point polymer component are partially melted to give nanofibers which give a surface coating effect. It can be produced a durable nanofiber without a process for a separate surface coating.
  • Nanofiber manufacturing method in the present invention is electrospinning, electro-spray, air electro-spinning, centrifugal electro-spinning, flash electrospinning (flash)
  • Various methods of spinning such as electro-spinning can be appropriately adopted and used.
  • the production of a laminated nanofiber web imparting a coating effect to the nanofibers according to the present invention is made by an air electrospinning (AES) method.
  • AES air electrospinning
  • the nanofiber web produced by the air electrospinning (AES) method has a low melting point of 50-170 ° C. and a nanofiber phase by electrospinning a high melting point polymer material having a melting point of 80-250 ° C. It comprises a nanofiber phase by the electrospinning of the polymer material.
  • the high melting point polymer material increases the mechanical properties of the nanofiber web
  • the low melting point polymer material plays a role of enhancing scratching and washing durability from the outside of the nanofiber web by partial melting.
  • polymer material used in the present invention electrospinning is possible, and examples thereof include hydrophilic polymers and hydrophobic polymers, and these polymers may be used alone or in combination of two or more thereof.
  • the polymer material usable in the present invention is not particularly limited as long as it is a polymer that can be dissolved in an organic solvent for electrospinning and can form nanofibers by electrospinning.
  • examples include polyvinylidene fluoride (PVdF), poly (vinylidene fluoride-co-hexafluoropropylene), perfuluropolymers, polyvinylchloride, polyvinylidene chloride or copolymers thereof, polyethylene glycol dialkyl Polyethylene glycol derivatives including ethers and polyethylene glycol dialkyl esters, poly (oxymethylene-oligo-oxyethylene), polyoxides including polyethylene oxide and polypropylene oxide, polyvinylacetate, poly (vinylpyrrolidone-vinyl Acetates), polystyrene and polystyrene acrylonitrile copolymers, polyacrylonitrile (PAN), polyacrylonitrile copolymers including polyacrylonitrile methyl methacrylate
  • Polyphosphazenes such as aromatic polyesters, polytetrafluoroethylene, polydiphenoxyphosphazenes, poly ⁇ bis [2- (2-methoxyethoxy) phosphazene] ⁇ , polyurethanes and polyetherurethanes Polyurethane copolymers, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and the like.
  • PVdF polyvinylidene fluoride
  • TPU thermoplastic polyurethane
  • PAN polyester sulfone
  • PS polystyrene
  • PVdF and PES polyvinylidene fluoride
  • PVdF and thermoplastic polyurethane (TPU) may be mixed, but are limited to the above materials.
  • PVdF polyvinylidene fluoride
  • TPU thermoplastic polyurethane
  • PAN polyester sulfone
  • PS polystyrene
  • PAN polyacrylonitrile
  • PVdF and PES PVdF and thermoplastic polyurethane
  • TPU thermoplastic polyurethane
  • the solvent is DMAc (N, N-Dimethyl acetoamide), DMF (N, N-Dimethylformamide), NMP (N-methyl-2-pyrrolidinone), DMSO (dimethyl sulfoxide), THF (tetra-hydrofuran), (EC (ethylene) carbonate), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), water, acetic acid, formic acid, chloroform, dichloromethane ( dichloromethane) and acetone (acetone) is characterized in that any one or more selected from the group consisting of.
  • the base material is any one or more selected from the group consisting of woven paper, nonwoven fabric, foam, paper, mesh, and the like.
  • the polymer material in order to form a fibrous structure, is preferably prepared in an amount of 5 to 22.5 wt% to control the morphology of the fibers.
  • the content of the polymer material is less than 5% by weight, it is difficult to form a fibrous shape, and even if particles are formed or spun, rather than spinning due to spraying, spraying is not performed. ) Is formed a lot, the volatilization of the solvent is not well made during the calendar process of the web melts the pore (pore) occurs. In addition, when the content of the polymer material exceeds 22.5% by weight, the viscosity rises, so that solidification occurs at the surface of the solution, which makes it difficult to spin for a long time.
  • the solvent mixed with the high molecular material may use a monocomponent solvent such as dimethylformamide (DMF), but in the case of using the bicomponent solvent, boiling point (BP) It is preferable to use a solvent mixed with a high and a low point).
  • a monocomponent solvent such as dimethylformamide (DMF)
  • BP boiling point
  • the two-component mixed solvent according to the present invention is preferably used by mixing a high boiling point solvent and a low boiling point solvent in a weight ratio of 7: 3 to 9: 1.
  • the high boiling point solvent is less than 7, there is a problem that the polymer is not completely dissolved, and when it exceeds 9, the low boiling point solvent is too small to volatilize the solvent from the spun fibers so that the formation of a web is smooth. The problem does not occur.
  • the two-component mixed solvent is, for example, DMAc (N, N-dimethylacetoamide: BP-165 ° C.) as a high boiling point solvent and acetone (acetone: BP-56) as a low boiling point solvent.
  • DMAc N, N-dimethylacetoamide: BP-165 ° C.
  • acetone acetone: BP-56
  • °C may be used by mixing in a weight ratio of 9: 1.
  • the mixing ratio between the two-component mixed solvent and the entire polymeric material is preferably set to about 8: 2 by weight.
  • the spinning solution dissolved in the solvent is air electrospun using a multi-hole spinning pack, and then a nanofiber web formed in a multi-layer is obtained and a thermal compression process, for example, calendaring, is performed.
  • a nanofiber web is obtained in which the low melting polymer on the surface is uniformly melted.
  • the method of forming the nanofiber web according to the present invention is realized using the air electrospinning apparatus shown in FIG.
  • nanofibers are radiated to the collector 6 by applying a high voltage electrostatic force of 90 to 120 KV between the spinneret nozzle 4 and the collector 6 on which the polymer solution having a sufficient viscosity is spun.
  • the fiber web 7 is formed, and in this case, by spraying air at each spinning nozzle 4, the spun fiber is caught in the collector 6 and blown off.
  • the air electrospinning apparatus of the present invention includes a spinning solution tank 1 in which a spinning solution in which a polymer material is mixed with a solvent is stored, and a plurality of spinning nozzles 41 to 44 connected to a high voltage generator (not shown). ) Includes a multi-hole spin pack 40 arranged in multiple columns / multiple rows.
  • the spinning pack 40 is disposed above the grounded collector 6 of the conveyor type moving at a constant speed, a plurality of spinning nozzles are arranged at intervals along the traveling direction of the collector 6, A plurality of spinning nozzles are arranged at intervals along a direction orthogonal to the traveling direction of the collector 6 (that is, the width direction of the collector). In FIG. 1, four spinning nozzles are arranged at intervals along the traveling direction of the collector 6 for convenience of description.
  • the radiation nozzles arranged along the traveling direction of the collector 6 may be arranged, for example, 30-60 or more, as required, and in the case of using a plurality of radiation nozzles, the collector 6
  • the productivity can be increased by increasing the rotational speed of.
  • the spinning solution tank 1 may have a built-in agitator 2 using a mixing motor 2a as a driving source to prevent phase separation until the low melting polymer material and the high melting polymer material are mixed with a solvent to form spinning. It is connected to the spinning nozzles 41-44 of each row through the metering pump and the conveying pipe 3 which are not shown from the spinning solution tank.
  • the first nanofiber web 7a is composed of fibers 51 in which the spinning solution is spun from the first spinning nozzle 41, and the second nanofiber web 7b is spinning solution from the second spinning nozzle 42.
  • the first nanofiber web 7a is composed of fibers 52 spun onto the top
  • the third nanofiber web 7c has a spinning solution from the third spinning nozzle 43 with the second nanofiber web 7b. It is made of a fiber 53 spun to the top of.
  • the spinning solution from the fourth spinning nozzle 44 is composed of the fibers 54 spun onto the third nanofiber web 7c to finally obtain a multi-layered nanofiber web 7 of four layers. have.
  • the first to third nanofiber webs 7a to 7c may be formed by stacked spinning of nanofibers by PVdF alone from three rows of spinning nozzles 41 to 43, and formed on top of the web formed from three rows of spinning nozzles.
  • a nanofiber web composed of two layers may be manufactured by stacking nanofibers in which PVdF and TPU are mixed from the fourth spinning nozzle 44.
  • the polymer spinning solution discharged sequentially from four rows of spinning nozzles 41 to 44 passes through the spinning nozzles 41 to 44 charged by the high voltage generator, respectively, and is discharged to the ultrafine fibers 5 to move at a constant speed.
  • Nanofibers are sequentially accumulated on the grounded collector 6 of the form to form a multilayer nanofiber web 7.
  • the air 4a is sprayed from a plurality of air injection nozzles (not shown) for each of the radiation nozzles 41 to 44 of each row using the multi-hole spinning pack 40.
  • the multilayer nanofiber web 7 is formed by an air electrospinning method.
  • the air injection may be simultaneously performed from the multi-hole spinning pack nozzle.
  • the air when the electrospinning is carried out by air electrospinning, the air is sprayed from the outer circumference of the spinning nozzle to play a dominant role in collecting and integrating the air, which is composed of a polymer having a high volatility, in the air. It is possible to produce high nanofiber webs and to minimize the radiation troubles that can occur as the fibers fly around.
  • the spin pack nozzle of the multi-hole spinning pack 40 used in the present invention is set in the range of 0.1 to 0.6 MPa when the air pressure of the air jet is, for example, 245 mm / 61 holes. In this case, if the air pressure is less than 0.1MPa, it does not contribute to the collection and accumulation. If the air pressure exceeds 0.6MPa, the cone of the spinning nozzle is hardened to block the needle, causing radiation trouble.
  • one of the spinning nozzles 41 of the first row and the spinning nozzles 42 of the second row is impossible to spin, or the web produced by the subsequent process may be formed from the web of the previous process. Adhesion may be degraded and separated.
  • the air electrospinning apparatus shown in FIG. 1 illustrates the formation of four layers of nanofiber webs 7 by four spinning nozzles 41-44.
  • the present invention provides a plurality of rows and columns.
  • As the high speed spinning and the high speed rotation are performed using the multi-hole spinning pack 40 having the spinning nozzles arranged, a nanofiber web having a multilayer structure made of ultra-thin films is obtained for each layer.
  • the multi-layer nanofiber web 7 is formed by air electrospinning, and in the thermocompression calendering process of the multi-layer nanofiber web, a heat compression roller (not shown) is used, in which case the calendering temperature is too low. If the web is too bulky to have rigidity, and if the temperature is too high, the web will melt during processing and the pores will be blocked.
  • the calendering temperature is a temperature at which the low melting polymer used may be partially melted, for example, about 50 to 170 ° C. It has a big influence on the performance of air permeability, moisture permeability, and water resistance according to the calendering temperature, and it has a big influence on the scratch resistance and the durability of washing according to the degree of partial melting of low melting point polymer.
  • the water resistance was measured using a low water pressure method according to ASTM D 751, and the air permeability was evaluated by ASTM D 737: 2004.
  • Preparation of the nanofiber composite using the laminated nanofiber web of the present invention can be prepared using a conventional fabrication method, preferably hot melt bonding, solvent bonding, thermal bonding, ultrasonic bonding, laser irradiation, high frequency treatment, Water jet and the like.
  • the physical properties of the nanofiber composite according to the present invention were evaluated for water resistance, water resistance after washing, air permeability, moisture permeability, and the results are shown in Table 2.
  • Figure 2 is a manufacturing process of the moisture-permeable waterproof fabric according to an embodiment of the present invention.
  • the spinning solution is put into the spinning solution tank 1 of FIG. 1 for air electrospinning to perform air electrospinning (S2), and the multilayer nanofiber web 7 is formed (S3).
  • the multilayer nanofiber web 7 thus formed is subjected to primary calendering as necessary (S4) and then dried (S5).
  • Primary calendering is to remove the solvent and water and compress the web.
  • secondary calendering S6 is performed to partially melt the low-melting polymer material to prepare a laminated nanofiber web given a coating effect.
  • the laminated nanofiber web prepared is subjected to lamination and maturing through the fabric and laminating process (S7).
  • Water-repellent finishing (S8) is carried out to the finished fabric to prepare a waterproof moisture-repellent fabric.
  • PVdF Polyvinylidenefluoride
  • a high melting point polymer was added to a mixed solvent of Acetone and DMAc (30:70 vol%) in 17wt%.
  • a spinning solution was prepared by dissolving to%, and a spinning solution was prepared by dissolving a low melting polymer TPU in DMAc to 12 wt%.
  • PVdF nanofiber web a high melting point polymer material
  • TPU nanofiber web a low melting point polymer material
  • nanofiber web thus prepared, solvent and water remaining on the surface of the nanofiber web by passing a primary line drying section in which 30 ° C air is circulated at a speed of 30 m / sec at 3 m / min was adjusted.
  • the nanofiber web thus adjusted was calendered when the calender rolls were heated to 50, 70 and 100 ° C, respectively.
  • FIG. 3 to 5 are scanning electron micrographs of nanofiber webs melted at different temperatures. From FIG. 3, when the temperature of the calender roll is 50 ° C., the nanofibers of the low melting point polymer component are hardly melted. In FIG. 4, where the temperature of the calender roll is 70 ° C., the nanofibers of the low melting point polymer component are partially melted. Shows the starting state.
  • FIG. 5 shows a state in which the nanofiber of the low melting polymer component is sufficiently melted when the temperature of the calender roll is 100 ° C. However, even in this case, it can be confirmed that the three-dimensional pore structure is maintained as it is.
  • Laminated nanofibers were prepared in the same manner as in Example 1, except that PVdF nanofiber web, a high melting point polymer material, was prepared with a basis weight of 5 gsm, and TPU nanofiber web, a low melting point polymer material, was used with a basis weight of 1 gsm. The web was prepared.
  • nanofiber web thus prepared, solvent and water remaining on the surface of the nanofiber web by passing a primary line drying section in which 30 ° C air is circulated at a speed of 30 m / sec at 3 m / min was adjusted.
  • the nanofiber web thus adjusted was calendered when the calender rolls were heated to 50, 70 and 100 ° C, respectively.
  • PVdF Polyvinylidenefluoride
  • a high melting point polymer was added to a mixed solvent of Acetone and DMAc (30:70 vol%) in 17wt%.
  • a spinning solution was prepared by dissolving to%, and a low melting point polymer material, TPU and PVdF, was blended, dissolved in DMAc, and dissolved to 13 wt% to prepare a spinning solution.
  • PVdF nanofiber web a high melting point polymer material
  • TPU nanofiber web a low melting point polymer material
  • nanofiber web thus prepared, solvent and water remaining on the surface of the nanofiber web by passing a primary line drying section in which 30 ° C air is circulated at a speed of 30 m / sec at 3 m / min was adjusted.
  • the nanofiber web thus adjusted was calendered when the calender rolls were heated to 100, 130 and 150 ° C, respectively.
  • a spinning solution was prepared such that the mixing ratio of the low melting polymer material used in Example 3 was 13 wt% (50:50 vol%) of TPU / PVdF.
  • PVdF nanofiber web a high melting point polymer material
  • TPU nanofiber web a low melting point polymer material
  • the solvent and water remaining on the surface of the nanofiber web by passing the first-line drying section where air at 30 ° C. circulates at a speed of 30 m / sec at 3 m / min was adjusted.
  • the nanofiber web thus adjusted was calendered when the calender rolls were heated to 100, 130 and 150 ° C, respectively.
  • Electrospinning was carried out by the method disclosed in the above to obtain a nanofiber web prepared with a basis weight of 6 gsm.
  • the nanofiber web prepared as described above was thermally compressed through the same process as in Example 1 except that calendering was performed when the calender roll was heated to 100 ° C., and then the water resistance, air permeability, The moisture permeability and the like were evaluated, and the results are shown in Table 1 together.
  • the low-polymerization polyurethane and the high-polymerization polyurethane used in Comparative Example 1 were dissolved in a mixed solvent of THF and DMAc (50:50 vol%) to 20 wt% and 15 wt%, respectively, to prepare respective spinning solutions.
  • the nanofiber web prepared as described above was thermally compressed through the same process as in Example 1 except that calendering was performed when the calender roll was heated to 100 ° C., and then the water resistance, air permeability, The moisture permeability and the like were evaluated, and the results are shown in Table 1 together.
  • Example 1 Table 1 division Basis weight (g / m 2 ) Calendering Temperature (°C) Air Permeability (CFM) Water resistance (mmH 2 O) High melting point material (PVdF) Low melting point material (TPU or TPU / PVdF)
  • Example 1 4 2 70 1.6 6000 4 2 100 1.3 8000
  • Example 2 5 One 50 1.8 4000 5
  • One 70 1.6 6000 5 One 100 1.4 7000
  • Example 3 100 1.5 6000 4 2 130 1.3 8000 4 2 150 1.2
  • Example 4 4 2 100 1.7 6000 4 2 130 1.6 7000 4 2 150 1.3 8000 Comparative Example 1 6 100 1.1 5000 Comparative Example 2 6 100 1.2 4500
  • FIG. 8 is a scanning electron micrograph showing a cross section of a nanofiber composite.
  • a nanofiber web and a base material cross-electrospun by Comparative Example 2 were passed through a calender roll heated at 100 ° C. with a nanofiber web and a base material to melt the nanofibers of a low melting polymer (low polymerization degree polyurethane) component.
  • the nanofiber composites were self-fused between the base fabric and the base fabric.
  • the water resistance, water resistance after washing, air permeability, moisture permeability, etc. of the nanofiber composite were measured in the same manner as in Example 5, and the results are shown in Table 2 together.
  • Example 1 70 1.2 6500 1500 100 1.2 8000 4500
  • Example 2 70 1.2 6000 1700 100 1.2 7500 3800
  • Example 3 100 1.2 6000 2500 130 1.1 8000 4500 150 1.0 8000 5500
  • Example 4 100 1.2 6000 2000 130 1.1 7000 4300 150 1.0 8000 5200 Comparative Example 3 100 0.8 4500 900
  • the present invention improves the fastness due to external factors in the nanofiber web and at the same time can adjust the pore structure to produce the desired material such as waterproof, moisture permeability, air permeability, heat insulation and light weight, filter material, biomedical, moisture absorption It can be applied to various types of clothing such as fabrics, outdoor clothing, military uniforms, NBC protective clothing, extreme cold protection clothing, and functional fabrics.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention porte sur une nanofibre stratifiée, sur un procédé pour sa production, sur des composites de nanofibres les utilisant et sur un procédé pour produire les composites, dans lesquels un film de nanofibres multicouche est produit par électrocentrifugation de polymères ayant des points de fusion différents, une substance polymère de couche supérieure ayant un bas point de fusion étant thermiquement comprimée de façon à faire fondre partiellement une surface du film de nanofibres et à produire ainsi des effets de revêtement, de façon à maintenir ainsi une résistance à l'encontre de rayures externes et une durabilité au lavage tout en obtenant également une excellente perméabilité vis-à-vis de l'air et de l'humidité.
PCT/KR2012/008983 2011-10-31 2012-10-30 Film de nanofibres stratifiés et procédés pour sa production et composite de nanofibres les utilisant Ceased WO2013066022A1 (fr)

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KR10-2011-0112442 2011-10-31

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WO2013066022A1 true WO2013066022A1 (fr) 2013-05-10

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WO2020096404A1 (fr) * 2018-11-08 2020-05-14 주식회사 아모라이프사이언스 Timbre de protection contre les ultraviolets et son procédé d'application
CN114712939A (zh) * 2022-03-22 2022-07-08 闽江学院 一种高精度多功能纳米水过滤材料及其制备方法

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CN114712939A (zh) * 2022-03-22 2022-07-08 闽江学院 一种高精度多功能纳米水过滤材料及其制备方法

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