JP2018150642A - Method of producing nanofiber laminate and thin film deodorizing shielding member for housing material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for producing a nanofiber laminate having air permeability, preventing entry of pollen, tiny insects and the like, and PM 2.5, absorbing unpleasant odors, allowing entry/exit of air and having optical transparency; and a shielding member.SOLUTION: There is provided a method for producing a nanofiber laminate including: producing a reinforced base material by spraying a first fibrous polymer adhesive on a strong base material which is a mono- or multi-filament woven or knitted fabric having a coarse mesh and, right after that, passing it through a cooling device to rapidly harden the first fibrous polymer adhesive, so as to reinforce mesh of the base material; spraying a second fibrous polymer adhesive, which needs a longer time to be hardened than the first fibrous polymer adhesive, on the reinforced base material so as not to block clearance of the mesh formed by the first fibrous polymer adhesive with 500 nm to 10 μm of fibrous diameter; spraying a nanofiber of polymer fiber on the thinly sprayed second fibrous polymer adhesive to laminate and bonding the reinforced base material to the nanofiber; and having air permeability and optical transparency so that the second fibrous polymer adhesive does not block the clearance of the nanofiber.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a nanofiber laminate, and a thin film deodorization shielding member for building materials using the same, and more particularly, a manufacturing apparatus for a thin film deodorization shielding member for building materials, which shields the outside air from the room. Manufacturing of nanofiber laminates that are used for breathable screen doors and agricultural houses that prevent pollen and fine insects from entering, absorb the odor of outside air, allow air to enter and exit, and transmit light A method and a thin film deodorizing shielding member for building materials using the method.

  Recently, nanofibers that are generally defined by fibers having a diameter of 1 micron (= 1,000 nm) or less have been developed. As a method for producing nanofibers, an ESD (Electro-Spray Deposition) method, or A technique called an electrospinning method has received the most attention, and the technique has been developed (see, for example, Patent Document 1). However, since the electrospinning method requires a high voltage, it is dangerous and difficult to handle.

Further, as a micro-order manufacturing method that is a conventional synthetic fiber that does not use a high-voltage electrode, Non-Patent Document 1 includes a sea-island composite spinning method, a low-viscosity molten polymer in addition to the electrospinning method described above. It has been disclosed that a melt-blow spinning method in which the polymer solution is blown off and a flash spinning method in which the polymer solution is rapidly expanded to solidify and fiberize while blowing off the polymer are disclosed. As a method for producing this ultrafine fiber only for melting, the above-mentioned Non-Patent Document 1 has a polymer blend spinning method as a method of spinning by dissolving in a solution. This is an ultra-fine spinning method that elutes a sea polymer, and μm is the limit.
Therefore, the inventors of the present invention succeeded in producing nanofibers by dissolving a polymer in a solvent so as to have a low viscosity as shown in Patent Document 2 and then drawing it with an air jet from an ultrafine nozzle and stretching it. Using this, a thin-film deodorizing shielding member that captures microparticulate matter PM2.5 that floats in the atmosphere deposited in the respiratory system and affecting health is manufactured.

  By the way, there is a screen door to keep air permeability and prevent mosquitoes, dead carcasses, dust, etc. from entering the room, but recently it can be removed to prevent extremely harmful substances such as pollen from entering the room. A screen door with a simple filter cover has been developed. Also, in agricultural houses, insect nets that have air permeability but do not allow minute insects or the like to enter have been developed as shown in Patent Document 3. Moreover, as shown in Patent Document 4, a screen door using a non-woven fabric mixed with titanium oxide to deodorize a strange odor has already been proposed. However, it is not a manufacturing method for manufacturing a thin film deodorizing shielding member that captures the fine particulate matter PM2.5 at a low cost.

JP 2011-127234 A JP 2014-144579 A Utility Model Registration No. 3034455 JP 2000-217446 A

SEN'I GAKKAISHI (Fiber and Industry) Vol.63, No.12 (2007) 423-425P [Development of melt-spun nanofiber] Takashi Ochi

However, since the screen door filter and the shielding member of the agricultural house mentioned above are non-woven fabrics of micro-order fibers at most, they must be laminated thickly in order to capture and shield the microparticulate matter PM2.5. Could not shield pollen.
In addition, since the nonwoven fabric is thick, there is a problem that the degree of light shielding is large, the room is dark, and the material cost is high.
On the other hand, a filter using nanofibers has been developed as a mask and other materials to shield pollen, etc., but nanofibers themselves are expensive and the nanofibers are sandwiched between substrates to hold them. There are inconveniences such as problems, and there are problems such as lack of strength.
An object of the present invention has been made in view of such problems, and has a breathability made of a nonwoven fabric of nanofibers, and a shielding member that captures microparticulate matter PM2.5 has sufficient strength. It is intended to provide a production method that has a sufficient deodorizing effect and is produced at low cost.
Moreover, the thin film deodorization shielding member for building materials which laminated | stacked the nanofiber of patent document 4 capture | acquires microparticulate matter PM2.5, but the adhesion durability of a nanofiber and the 1st, 2nd fibrous polymer adhesive However, when used outdoors for a long period of time, there is a problem of durability that the nanofiber laminate is peeled off from the base material, and there is also a problem with the durability of the deodorizing effect. It is an object of the present invention to provide a manufacturing method that overcomes this point.

  In order to solve the above-mentioned problems, the invention of claim 1 is characterized in that a first fibrous polymer adhesive is applied to a base material having a coarse eye strength with a mono- or multi-filament knitted fabric by a first adhesive spray. The first fibrous polymer adhesive is rapidly cured by spraying on the material and immediately passing through a cooling device to form a finer mesh in the base of the base material to form a reinforcing base. The base and the reinforcing base A second fibrous polymer adhesive having a curing time slower than that of the first fibrous polymer adhesive was formed with the first polymer adhesive to a fiber diameter of 500 nm to 10 μm by an adhesive spray. The nanofiber spray is made of a polymer material nanofiber having a long molecular arrangement on the second fiber-like polymer adhesive, which is thinly sprayed on the net and contracted so as not to block the gap. By spraying and laminating, the base material, the reinforcing base material, and the nanofiber are bonded to each other, and the second fibrous polymer adhesive does not block the gap between the nanofibers so that air permeability and light transmission can be achieved. It is a manufacturing method of the nanofiber laminated body characterized by having property.

Invention of Claim 2 is the manufacturing method of the nanofiber laminated body of Claim 1, The nozzle of the said nanofiber spray was made into the ceramic or the ruby.
Invention of Claim 3 is a manufacturing method of the nanofiber laminated body of Claim 1 to 2, In the nanofiber laminated body, the titanium oxide was sprayed as a deodorizing material, It is characterized by the above-mentioned.
Invention of Claim 4 is a manufacturing method of the nanofiber laminated body of Claim 3, In the said titanium oxide, the said polymer fiber is made into 2-20 weight with respect to this polyvinylidene fluoride as polyvinylidene fluoride (PVDF). % Titanium oxide was sprayed as a deodorant and adhered.
The invention of claim 5 is the method of laminating nanofibers selected from the claims 1 to 4, wherein the mono or multifilament is 0.1 to 0.5 mm diameter polypropylene (PP), Coarse eyes of the woven or knitted fabric made of filaments are 15 to 30 mesh.
The invention according to claim 6 is the method of laminating nanofibers selected from claims 1 to 5, wherein the first fibrous polymer adhesive is a fiber having a fiber-like diameter of 10 μm to 100 μm. And the first fibrous polymer adhesive is rapidly cured by passing through a gap of a cooling plate of a cooling device disposed immediately downstream.
The invention of claim 7 is the method for producing a nanofiber laminate according to claim 6, wherein the cooling device is constituted by a thermocouple, and the surface temperature of the cooling plate is set to -10 ° C to -20 ° C. And
The invention according to claim 8 is the method of laminating nanofibers selected from claims 1 to 7, wherein the first fibrous polymer adhesive forms a network, and the base material and the fiber-like layer are formed. (2) It is characterized by adhering to a polymer adhesive and nanofiber so as not to form a film.
The invention of claim 9 is the method of laminating nanofibers selected from claims 1 to 8, wherein the nanofiber generator of polymer fibers before the sprayed second fibrous polymer adhesive is cured The nanofiber laminate produced from the above is sprayed, and further, titanium oxide is sprayed and then wound.

  According to the invention of claim 10, the first fibrous polymer adhesive is sprayed on the base material by the first adhesive spray on the base material having the coarse eye strength with a mono- or multifilament woven or knitted fabric, and immediately after that, the cooling device And the first fibrous polymer adhesive is rapidly solidified to form a finer web of mesh in the eye of the base material to form a reinforcing base material. Slowly slower than the fiber-like polymer adhesive, the second fiber-like polymer adhesive has a fiber-like diameter of 500 nm to 10 μm and does not block the gaps of the network formed by the fiber-like first polymer adhesive. The second fiber is bonded to the reinforcing substrate and the nanofiber by spraying and laminating the nanofiber of the polymer fiber onto the second fiber-like polymer adhesive sprayed thinly. Jo polymer adhesive not block even clearance of the nanofibers is thin deodorizing shielding member for building material characterized by using the nanofiber laminate having a permeability and light transmittance.

According to the method for producing a nanofiber laminate of the present invention and the thin-film deodorizing shielding member for building materials using the nanofiber laminate, the nanofiber laminate has sufficient strength despite being a thin shielding member, and has increased durability. There is little peeling between the fiber laminate and the base material, it has sufficient air permeability, lowers the light shielding rate, prevents the entry of pollen particles and fine insects, increases its collection efficiency, and smells like ammonia gas Can be efficiently decomposed and its deodorizing effect can be maintained for a long time.
In addition, if the material of the nanofiber is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is also a resin that is resistant to radiation, so it is also suitable as a building material for screen doors and agricultural houses deployed outdoors. Cleaning is also easy.
Furthermore, since the spray nozzle for adhesives and nanofibers is ceramic or ruby, the center outlet is heat resistant, durable, less deformed, and nanofibers even when high temperature heated polymer fibers are spun for a long time. There is no deformation, and a uniform nanofiber diameter can be maintained.
Furthermore, the thin-film deodorizing shielding member for building materials laminated with nanofibers is a collection that is thin and strong, has sufficient air permeability, has a low light shielding rate, and prevents entry of pollen particles and fine insects. Increases efficiency, has sufficient strength, efficiently decomposes off-flavors such as ammonia gas, and can be manufactured in large quantities at low cost.

Overall conceptual schematic diagram of the nanofiber laminate production method of the example in the present invention, Sectional view of the first (second) polymer adhesive nozzle of FIG. The enlarged view of the nozzle of FIG. Sectional drawing of the molten resin introduction pipe | tube 23 in the X1-X1 line | wire of FIG. 1 is a cross-sectional view of the cooling device of FIG. FIG. 5 is an explanatory diagram of the Peltier device. Description partial cross-sectional view of the nanofiber generation step E1 of FIG. The enlarged view of the nozzle of FIG. Explanatory drawing of the deodorant spraying device of FIG. The micrograph figure of only base material N1 in the example of the present invention, FIG. 10 is a photomicrograph of the base material N1 and the reinforcing base material N2 that were passed through the cooling device that was operated by spraying the first polymer adhesive N2 on the base material N1. FIG. 10 is a photomicrograph of the substrate and the reinforcing substrate N2 when the first polymer adhesive N2 is sprayed onto the substrate N1 and the cooling device is not operated. FIG. 11A is a photomicrograph of the second polymer adhesive N3 sprayed on the substrate N1 and the first polymer adhesive N2 sprayed on the example of FIG. The photomicrograph from the nanofiber side in the state where the nanofiber N4 in the state where the second polymer adhesive N3 is sprayed on the base material N1 and the first polymer adhesive N2 is laminated on the substrate of FIG. Figure, In the state of FIG. 13 in the embodiment of the present invention, a micrograph of a state in which the nanofiber N4 is laminated by spraying the second polymer adhesive N3 on the base material N1 and the first polymer adhesive N2, and the deodorant is sprayed and fixed. Figure.

A feature of the present invention is a method for producing a nanofiber laminate in which a nanofiber laminate of 1 μm (micron) or less is adhered and fixed to a base material, and a thin film deodorization shielding member such as a filter for building materials using the nanofiber laminate, Specifically, a base material having a coarse mesh strength with a mono or multi-filament knitted fabric is sprayed onto the base material with a first adhesive material having a fiber diameter of 10 to 100 μm thicker than nanofibers. In addition to improving the adhesion with finer spider web-like fibers and reinforcing the strength of the nanofiber, the reinforced base material has a fiber diameter of 10 μm to 100 nm, which is slightly thicker than the nanofiber. Thinly sprayed on the base material reinforced with the material so as not to block the gap, and the nanofiber is laminated on the second adhesive to bond the base material and the nanofiber. In order to increase the durability of the adhesion, it is characterized by spraying to increase the fast-drying first adhesive adhesion strength, and immediately after cooling with a cooling device. The 2nd adhesive which requires time is wound up after running a long distance after spraying nanofibers.
Below, the manufacturing method of the nanofiber laminated body of this invention and the thin film deodorizing shielding member for building materials using the same are demonstrated with reference to drawings of the Example.

A method for producing a nanofiber laminate in Example 1 of the present invention and a thin-film deodorizing and shielding member for building materials using the same will be described with reference to a conceptual explanatory diagram showing the overall outline of FIG.
As shown in FIG. 1, the outline of the nanofiber laminate manufacturing apparatus is in the following process order. First, the first step is a step of feeding out the base material N1 woven with monofilament [base material feeding step A], and the next step is to spray the first polymer adhesive N2 on the fed base material and use the first adhesive fiber A step of forming a nest-like or zigzag net portion and adhering to the base material to reinforce the base material [net-like reinforcing fiber forming step B], spraying the first fibrous polymer adhesive N2 and applying the first adhesive fiber A step of cooling [first polymer adhesive cooling step C], a step of spraying a second fibrous polymer adhesive N3 for further bonding the second adhesive nanofibers to the reinforced substrate to form an adhesive part [first 2 polymer adhesive spraying step D], a step of spraying nanofiber N4 onto this polymer adhesive N3 [nanofiber generation step E], a step of spraying a deodorant onto this nanofiber [deodorant attaching step F], Deodorants Is constructed from a step [nanofiber laminate winding process G] winding the product nanofibers N5 which spraying. Therefore, each process described above will be described in detail sequentially.

[Substrate feeding process A]
The simple substance of the base material N1 of this example is as shown in FIG. 10 of the micrograph, and is woven with a 0.25 mm diameter PP (polypropylene) monofilament used for a normal screen door, and 1 inch (25.4 mm). ) 18 mesh net with 18 squares x 18 squares (Dio Kasei Co., Ltd. insect repellent net (product number mesh 18)), thickness is 0.48mm, weight is 80g / m2, The base material is sufficiently strong to be used as a building material such as a screen door. As the substrate N1, polyethylene (PE), polyester (PET), polyphenylene sulfide (PPS), etc. may be used other than the above PP (polypropylene), and the diameter of the mono or multifilament is 0.1 to 0.1. The mesh having a diameter of 0.5 mm and the woven or knitted fabric made of mono- or multifilaments may have a mesh of 15 to 30 mesh.
As shown in FIG. 1, the base material N1 has a roll-shaped take-up rod 11 set in the base material (N1) supply section 1 in the region [A], and is pressed downward from the take-up rod 11. Then, the feed roller 12 passes through a plurality of guide rollers 13 and a tension adjusting mechanism 14 to be sent to the next step [net-like reinforcing fiber forming step B].

[Reticulated reinforcing fiber formation process B]
The network reinforcing fiber forming portion 2 in the network reinforcing fiber forming step B sprays the first polymer adhesive N2 on the substrate N1 to be sent out, and forms a network by crosslinking with a spider web or zigzag fiber, In addition to preventing the mesh weaved of the base material N1 from shifting, further forming a finer mesh in the mesh space of the base material N1 to reinforce the strength of the thin nanofiber layer to be laminated in the subsequent process , Preventing the nanofiber layer from breaking.
This state is as shown in FIG. 12 of the photomicrograph, and the space portion of the square mesh in the base material N1 is 10-100 μm thick on average with the first nanofiber-like polymer adhesive, and is thicker than the nanofiber N4. The fibers are cross-linked and stretched to form a finer mesh (N2), and the nanofiber layer N4 in the subsequent process is formed into a second nanofibrous polymer adhesive. The strength of the nanofiber laminate is improved by bonding (N3) with this adhesive.

This first fibrous polymer adhesive N2 is an adhesive for cross-linking and reinforcement (manufactured by Co., Ltd .; KLEIBERIT PUR reactive hot melt (product number: No. 703.5)) and extends so as to draw a thread in a spider web shape. The adhesive of the first polymer adhesive does not need to be heated and gradually cures at room temperature (several seconds). And no alteration to the nanofiber N4.
However, even if the first fibrous polymer adhesive N2 is quick-drying, it is not completely cured, that is, the base N1 and the second polymer adhesive N3 and nanofibers N4 are fixed in the subsequent process. It was not sufficient and often peeled off.
For this reason, even if the first fibrous polymer adhesive N2 is quick-drying, it is necessary to complete the solidification (curing) completely until it moves to the next step. A step of cooling the first fibrous adhesive by spraying the first fibrous polymeric adhesive N2 to be described [first polymeric adhesive cooling step C] is provided.
The reason why the first polymer adhesive N2 forms a spider web or a zigzag network in the space of the square network in the base material N1 is that the space formed by the nanofibers N4 is less blocked. Therefore, if the space of the mesh is reduced with the monofilament itself of the base material N1, not only the weight of the shielding member is increased, but also the disadvantage that the light shielding rate is increased occurs.

The net-like reinforcing fiber forming portion 2 for stretching the spider web-like or zigzag-like fibers will be described with reference to FIGS.
As shown in FIG. 1, the net-like reinforcing fiber forming portion 2 is located between [base material feeding step A] and [first polymer adhesive cooling step C], and is a polypropylene (or polypropylene) base. Since the first polymer adhesive N2 is sprayed on the surface of the material N1 to form a fine mesh in the square space of the substrate N1, the nanofiber N4 and the second polymer adhesive N3 are bonded. Immediately before the agent is sprayed onto the base material N1, as shown in FIGS. 2 and 3, the nozzle part 22 is sprayed on the base material N1 in a fiber shape slightly thicker and stronger than the nanofiber.

This first fibrous polymer adhesive N2 is a polyurethane hot melt adhesive (moisture curing type) (PUR Reactive Hot Melt (Part No.) No. 703.5) manufactured by Kleiberit Japan Co., Ltd. and has the following physical properties It is.
(A) Main component Polyurethane Viscosity
120 ℃: 11,000 mPas
140 ℃: 6,000 mPas
Open time (deposition (curing) time to evaporate the solvent) φ3mm bead: 30sec Open time 90μm: 30sec
Features: heat resistance, water resistance, cold resistance, low temperature coating, elastic type, stringiness

When the first fiber-like polymer adhesive N2 is sprayed, if the gap between the nanofibers N4 is filled, good air permeability of the folded nanofibers N4 is hindered. It is important that the agent N2 is formed as thin as possible so as not to fill the gaps of the nanofibers N4 so as to form a spider web or zigzag net.
The first fibrous polymer adhesive N2 was PUR reactive hot melt ((product number) No. 703.5).
(1) The reinforcement of the mesh space (between meshes) of the base material N1 and the expansion of the adhesive application surface of the second polymer adhesive N3 described later (expansion of the bonding area) can be measured, and (2) in a fiber shape (3) The distance from the first polymer adhesive spraying step to the second nanofibrous polymer adhesive N3 spraying step is short, so that the bonding is strong. It is necessary that the surface be cured immediately after application of the agent. As the other first polymer adhesive N2, the same result was obtained with a non-yellow discoloring type (transparent or white) polyurethane hot melt adhesive (moisture-curing type) manufactured by Kleiberit Japan Co., Ltd. was gotten.

In FIG. 1, the spraying portion 21 of the first fibrous polymer adhesive N2 of the mesh reinforcing fiber forming portion 2 is disposed above the base material N1 from the upper guide roller 13a to the lower guide roller 13b. Are reciprocated at a distance of 110 cm (nanofiber generation width) parallel to the surface of the substrate N1 that moves together. This is because the first polymer adhesive N2 does not need to be laminated like the nanofiber layer, and the strength of the nanofiber N4 only needs to be reinforced, and it is preferable that the first polymer adhesive N2 be less.
The first nanofibrous polymer adhesive N2 has a lower viscosity at a higher temperature and a viscosity at 140 ° C. of 6000 (mPa · s). 22 is provided with a heater (heater) 264. The first fibrous polymer adhesive N2 needs to be fast-drying (several seconds) so as to melt and fuse with the second fibrous polymer adhesive N3 described later.

Here, the details of the polymer resin spraying part 21 and the nozzle part 22 of the first fiber-like polymer adhesive N2 (adhesive) will be described with reference to FIGS. The heated adhesive (first polymer adhesive N2) supply unit 24 supplies the central nozzle 221 having a tip nozzle diameter of 0.15 mm from an adhesive (first polymer adhesive N2) supply pipe 241 by a supply pump 242. The A tubular hot air blowing part 26 is provided so as to wrap the outer cylinder at the tip of the central nozzle 221, and the high-temperature heated air H is injected from the hot air blowing nozzle part 261 of the hot air blowing part 26 to melt from the central nozzle 221. The nanofiber polymer adhesive N2 is sprayed toward the base material N1 so as to be pulled out. At this time, the air pump 28 that blows the high-speed heated air H supplied to the hot air blowing nozzle portion 261 is heated at 50 liters / minute through the heated air generator 281, the heated air supply pipe 282, and the heated air introduction portion frame 272. The high-speed heated air H is introduced into the high-speed air blowing passage formed between the forming cap 27 and the molten resin introduction pipe 23 and is connected to the high-temperature high-speed blowing passage from the hot air blowing nozzle portion 261 at the tip of the heated high-speed air blowing outlet 263. Erupted.
The air blowing nozzle part 261 has a jetting area of about 1 mm ² and the entire nozzle part 22 is adjusted to a high temperature by a heater 264 at about 140 ° C., and the jet air is also heated to about 140 ° C. and jetted. The temperature at 140 ° C. is maintained even at the tip of 22. It should be noted that it is desirable to provide a nozzle wind tunnel 29 at the tip of the heated air passage forming cap 27 so that the jet air does not turbulent from the outside near the tip of the nozzle portion 22.

Further, as described above, the outer peripheral portion 231 on the downstream side of the molten resin introduction pipe 23 having the molten resin introduction path 234 continuous with the nozzle portion 22 of the adhesive is provided with the hot air introduction groove 232 continuous with the nozzle portion 22. The hot air introduction groove 232 communicates with the hot air generator 281 at the other end.
As shown in FIG. 4, the hot air introduction groove 232 is obtained by cutting the outer peripheral portion 231 of the molten resin introduction pipe 23 having a circular cross section into a flat shape. In this embodiment, four long hot air introduction grooves 232 are formed. Yes. The hot air introduction grooves 232 are preferably configured to face each other, and this blows out the hot air facing from the nozzle portion 22 of the high-speed hot air blowing, so that it acts to stretch the molten polymer material of the adhesive. Further, since the long hot air introduction groove 232 is formed, hot air is blown out from the nozzle portion 22 in an orderly manner.
With such a configuration, it is found that the adhesive is produced in a large amount in the form of fibers having a fiber diameter of 500 nm to 500 μm, although it is somewhat thicker than this method without using the ESD method. The first polymer adhesive N2 melted in a fiber shape of 100 μm is sprayed on the polypropylene substrate N1 so as to stick in a spider web or zigzag form, and is uniformly applied to the whole.

The nozzle body 221 is provided with a ring-shaped high-speed hot air blowing passage 262 coaxially around the central shaft hole 2211 so as to wrap around the central shaft hole 2211, and a predetermined blowing angle is provided at the tip of the high-speed hot air blowing passage 262. A ring-shaped high-speed air outlet 263 having a nozzle is provided, and the discharge port 2212 of the nozzle body 221 slightly protrudes from the high-speed air outlet 263 by about X = 3 mm (2 to 4 mm) so that rectification occurs.
As shown in FIG. 3, the amount X of protrusion of the discharge port 2212 from the high-speed air outlet 263 is such that the high-speed hot air outlet passage 262 of the heated air passage forming cap 27 is skewed, and the central nozzle body 221 Since the outer periphery is also skewed, a fine adjustment washer 273 for the hot air outlet is interposed between the heated air passage forming cap 27 and the heated air introduction part frame 272, and the different thicknesses of the fine adjustment washer 273 are different. The amount of protrusion X can be adjusted by selecting one or adjusting the number of sheets. This can finely adjust the opening area of the hot air blowing nozzle portion 261 between the inner wall of the hot air blowing passage 262 and the outer periphery of the nozzle body 221 at the same time as adjusting the protrusion amount X.
Thus, since the hot air blowing amount of the hot air blowing nozzle portion 261 can be finely adjusted, the hot air blowing amounts of the plurality of nozzle portions 22 can be made the same as shown in FIG. A laminate of the nanofibers of the agent and the molecular material can be produced.

Further, the nozzle portion 22 mainly comprises a nozzle body 221 and a nozzle support 222, and as shown in an enlarged view in the vicinity of the discharge port 2212 in FIG. 3, molten polymer is ejected to the nozzle body 221 in the longitudinal direction. A central shaft hole 2211 is provided, and a discharge port 2212 is provided at the downstream end of the central shaft hole 2211. What is important here is the material of the nozzle body 221, but the material of the nozzle body 221 in the spinning nozzle portion 22 of the present invention is optimally ceramic or ruby, and in this embodiment is ruby.
The nozzle inner diameter of the discharge port 2212 is 0.13 mm to 0.18 mm. However, when it is 0.18 mm or more, it is difficult to form nano-unit fibers, and when it is 0.13 mm or more, the polymer adhesive melted to the nozzle inner diameter. In this embodiment, the thickness is about 0.15 mm. Further, in Patent Document 4 of the prior art, the nozzle inner diameter is set to 0.15 mm, but since the material is metal stainless steel, it has been found that the nozzle is immediately transformed into a thick fiber. It has been found that this is due to the expansion of the inner diameter of the stainless nozzle due to repeated loading and pressure. For this reason, when using a ruby (ceramic) that has excellent heat resistance and wear resistance and does not deform even at high temperatures, a high-quality polymer nanofiber laminate N5 could be produced even after continuous operation for a long time.
Since the base material N1 is rough, the first fibrous polymer adhesive N2 passes through the base material N1, and is collected by the adhesive collecting unit 25 behind.

However, ceramic and ruby are difficult to process, and it is difficult to fix the nozzle discharge port 2212 to the metal nozzle support 222 provided with screws or the like with screws or the like. Therefore, as shown in FIG. 3, a thick flange portion 2213 protruding outward is provided at the upstream end of the nozzle body 221, and the protrusion protruding inward at the downstream end of the corresponding inner hole 2221 of the nozzle support 222 is provided. A stop portion 2222 is provided, and the nozzle body 221 is inserted from the opening 2223 upstream of the inner hole 2221 of the nozzle support 222, and the flange portion 2213 is closely fitted and fixed to the locking portion 2222. With such a structure, the nozzle main body 221 does not separate from the nozzle support 222 even when the molten polymer is inserted at a high pressure downstream. In this case, the inner diameter of the inner hole 2221 is larger than the outer diameter of the nozzle body 221 and the outer diameter of the flange portion 2213, and the inner diameter of the tip locking portion 2222 of the nozzle support 222 is smaller than the outer diameter of the nozzle body 221. It is necessary to make it smaller than the outer diameter of the portion 2213.
Further, the molten resin is supplied to the molten resin introduction pipe 23 communicating with the nozzle portion 22 by an appropriate means. For example, as shown in FIG. 2, the supply pump 242 and the adhesive are supplied from the adhesive supply portion 24. Connected by a supply pipe 241 and supplied.
If the nozzle main body 221 moves while maintaining the same distance in the horizontal direction with respect to the base material N1 as necessary, the number of nozzle main bodies 221 can be reduced.
Next, the process proceeds to [first polymer adhesive cooling step C] in order to cool the first fibrous polymer adhesion.

[First polymer adhesive cooling step C]
In this embodiment, the cooling device 4 in [first polymer adhesive cooling step C] uses a Peltier element.
As shown in FIG. 5, the cooling plate 31 made of an aluminum plate is cooled to a surface temperature of −10 ° C. to −20 ° C., and a heat insulating plate 32 is disposed opposite to the cooling plate 31 so that the interval is 5 mm or less. The first fiber-like polymer adhesive N2 may have a distance of 1.5 mm or less between the network reinforcing fiber obtained by applying the first fiber-like polymer adhesive N2 to the substrate N1 in the previous step and the cooling plate 31. It is also preferable from the viewpoint of promoting the curing of the resin and saving energy.
A cooling mechanism 33 for the Peltier element is incorporated behind the cooling plate 31. The principle of the Peltier element is as shown in FIG. 6, and the Peltier device 34 is composed of, for example, a plurality of Peltier elements, and a plurality of N The type thermoelectric semiconductor (n) 341 and the P type thermoelectric semiconductor (p) 342 are alternately arranged, connected in a zigzag manner by the metal electrodes 343, and a DC power source from the power source 345 is supplied to both ends. Yes. In this connection state, as shown by the right-pointing arrow in FIG. 6, electrons and holes in the semiconductor carry heat downward, so that the left metal electrode 343u is cooled and the right metal electrode 343d is heated.
A plurality of upper surfaces of the left metal electrode 343u are connected to each other and covered with a thin plate-like insulating material 344, and are overlapped through the insulating material 344 so as to be in close contact with each other so as to conduct heat efficiently. ing. Similarly, a plurality of upper surfaces of the right metal electrode 343d are connected to each other and covered with a thin insulating material 344, and heat is efficiently conducted to the cooling plate 31 that cools (heat absorption) (heat generation) through the insulating material 344. They are layered in close contact.
This [first polymer adhesive cooling step C] is very important, and the microphotograph when this [first polymer adhesive cooling step C] is passed through is shown in FIG. Fig. 11B is a photomicrograph of the case where the [first polymer adhesive cooling step C] does not exist (does not operate) while it is reinforced with a spider web-like mesh, and the second adhesive is shrunk. Since it is not a spider web, it can be seen that it is not a strong reinforcement.
A step of spraying a second fibrous polymer adhesive N3 for adhering the second adhesive nanofibers after the solidification (curing) of the adhesive is promoted for the substrate N1 reinforced with a net-like structure [second polymer adhesive The process proceeds to spraying step D].

[Second polymer adhesive spraying step D]
Next, a second fibrous polymer adhesive N3 for adhering nanofibers is sprayed on the substrate reinforced with the first fibrous polymer adhesive N2 in [Reticulated reinforcing fiber formation step B] [second polymer. The adhesive spraying process D] will be described.
This state is as shown in FIG. 12 (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3) of the micrograph, and the fibers having a thickness of 10 μm to 100 nm, which is thinner than the first fibrous polymer adhesive N2. The second fibrous polymer adhesive N3 having a diameter is thinly sprayed onto the net so that the gap is not closed. As described above, the second fibrous polymer adhesive N3 adheres and shrinks in a state where the adhesive N2 is attached to the base material N1.
Therefore, compared to the state of the first fibrous polymer adhesive N2 (base material N1 + crosslinked adhesive N2) in FIG. 3, the micrograph in FIG. 13 shows that the adhesive of the second polymer adhesive N3 It is sprayed thinly so as not to block the gap.
As shown in FIG. 1, the apparatus configuration of [second polymer adhesive spraying step D] is located between [first polymer adhesive cooling step C] and [nanofiber generation step E], and the nozzle Is basically the same as [Reticulated reinforcing fiber forming step B], and the second fibrous polymer adhesive is bonded to the surface of the polypropylene (or polypropylene) substrate N1 and the first polymer adhesive N2. Spray the adhesive of agent N3.

This second fibrous polymer adhesive N3 is a polyurethane hot melt adhesive (moisture-curing type) (PUR reactive hot melt (product number) No. 701.1 or 701.2) manufactured by Kleiberit Japan Co., Ltd. It ’s like that. In this example, UR reactive hot melt (product number) No. 701.2 was used. In addition, as the other second polymer adhesive N3, the same result was obtained with a non-yellowing discoloration type (transparent or white) polyurethane hot melt adhesive (moisture curing type) manufactured by Henkel Co., Ltd. .
(B) PUR reactive hot melt (Part No.) No. 701.1 Main component Polyurethane Viscosity
80 ℃: 12,000 mPas
100 ℃: 4,000 mPas
120 ℃: 2,000 mPas
Open time:> 1 hour
Green strength: Strong Features: Low temperature coating, no stringing, hydrolysis resistance (C) PUR reactive hot melt (product number) No. 701.2 Main component Polyurethane Viscosity (during manufacturing)
brookfield HBTD 10rpm 100 ° C About 5,000 ± 1,500mPas 120 ° C About 3,000 ± 1,000mPas Open time. φ3mm bead: 3-4sec Additive: Contains isocyanate.

The second polymer adhesive N3 was a PUR reactive hot melt (product number: No. 701.1 or 701.2).
(1) Adhesiveness between the mesh space of the substrate N1 (between meshes) and the substrate of the reinforcing mesh formed by crosslinking of the first polymer adhesive N2 is good, (2) without closing the mesh, Less deformation such as stringiness, (3) a long time until the surface is cured after the second polymer adhesive N3 is applied, and a relatively long time until the surface is cured (3 minutes to 1 Time) to apply the nanofibers and maintain a long time for the base material N1 and the nanofibers N4 to be bonded and cured. (4) Before the curing, the adhesive is strong and the main component of the deodorant is It is necessary that the nanofibers N4 sprayed with titanium oxide be easily adhered.
Therefore, other polymer adhesives may be used as long as they satisfy these conditions and can form a fiber having a fiber diameter of 500 nm to 10 μm.

The nozzle device using this is the same as in [Reticulated reinforcing fiber forming step B], only the polymer adhesive to be supplied is different.
This second polymer adhesive N3 is an adhesive (second fiber polymer adhesive N3) that adheres and fixes the first fiber polymer adhesive N2 and the nanofiber N4 to the substrate N1, and has an adhesive property. It has stronger properties and is convenient for fixing the nanofiber N4 laminate to the substrate N1. In addition, since the second polymer adhesive N3 adhesive does not need to be heated and is gradually cured at room temperature, the base fiber N1 and the nanofibers N4 sprayed with titanium oxide are not altered.
In addition, the reason why the second fiber-like polymer adhesive N3 forms a spider web or zigzag network in the space of the network such as the base N1 is that the space formed by the nanofiber N4 is blocked. This is because, unlike the case of reducing the mesh space with the monofilament itself of the base material N1, the weight of the shielding member is increased and the light shielding rate is increased. .

As described above, it is important that the second fibrous polymer adhesive N3 is formed into a sufficiently thin fiber shape so that the space formed by the nanofiber N4 is not blocked as much as possible. The use of the adhesive in the shape eliminates the meaning of using the nanofiber N4, and it is preferable that the fiber be as thin as possible. In this embodiment, it is important that the second polymer adhesive N3 is made of a fiber having a fiber diameter of 500 nm to 10 μm, and is thinly blown and easily contracted so as not to block the gap.
In short, the first fiber-like polymer adhesive N2 and the second fiber-like polymer adhesive N3 are absolutely required to form thin fibers, but in particular, the first fiber-like polymer adhesive N2 is a mesh. Therefore, it is desirable that the fiber (fiber) -like shape be cured immediately while having an adhesive function. Conversely, the second fibrous polymer adhesive N3 is composed of the base material N1 and the first fiber. It is desirable to improve the function of bonding the polymer adhesive N2 and the nanofiber N4, maintain a sufficient bonding time, and cure relatively slowly. As shown in FIG. 1, this embodiment is also configured to shift a sufficiently long distance before winding.
That is, in this embodiment, the distance from the adhesive supply section 24 to the nanofiber laminate winding section 7 is 10 to 20 m, and the moving speed of the base material N1 is 80 cm / min to 150 cm / min. In this case, the distance from the adhesive supply part 24 to the nanofiber laminate winding part 7 is 15 m, the moving speed of the substrate N1 is 100 cm / min, and the second fibrous polymer adhesive N3 is slowly cured. I try to keep enough time.
As described above, the structure and setting conditions of the nozzle of the first polymer adhesive N2 itself are as shown in FIG. 8 simply by changing the first fiber polymer adhesive N2 to be supplied to the second fiber polymer adhesive N3. Although the structure itself is the same as that of the nozzle part 22 and the air blowing nozzle part 261 of FIG.2 and FIG.3 except the 2nd polymer resin spraying part 21b, description is abbreviate | omitted.

[Nanofiber production process E]
The nanofiber generation process E mainly includes a nanofiber generation process E1 and a nanofiber collection process E2.
[Nanofiber generation process E1]
[Second polymer adhesive spraying step D] is completed, and a state as shown in FIG. 12 of the microphotograph (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3) [nanofiber generating part D] The nanofibers of polyvinylidene fluoride (PVDF) produced in step 1 are sprayed and laminated.
This state is a photomicrograph as shown in FIGS. 13 and 14 (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3 + nanofiber N5 dispersed with titanium oxide).
The apparatus configuration of [Nanofiber generation step E1] of [Nanofiber generation part E] will be described. In this nanofiber generation step E1, the configuration of the nozzle portion is substantially the same as that of the reticulated reinforcing fiber formation step B. The difference is that, in order to stretch the raw material polymer, the polymer is melted with a solvent and thinned by viscosity instead of melting at a temperature like an adhesive. Since the material is dissolved in a solvent and pressurized and spun from a spinning nozzle, it does not need to be heated to a high temperature like an adhesive, but it must be maintained at about 30 ° C to 38 ° C, and high-speed air for stretching is also hot. There is no need to heat it. Here, the spinning nozzle unit 4 will be described first.

[Nanofiber spinning nozzle]
In the nanofiber spinning nozzle, the polymer material is not melted but melted, and the operating temperature is 30 ° C to 38 ° C, which is different from heating and melting the polymer material of the adhesive at about 300 ° C. The configuration is basically the same as that of the adhesive nozzle portion 22 described above.
As shown in the enlarged view of the nozzle portion 42 of the nanofiber spraying portion 41 in FIGS. 7 and 8, the nozzle body 421 of ceramic, particularly ruby, is provided with a central shaft hole 4211 following the discharge port 4212 at the tip, A feeding port 43 is provided on the opposite side of the shaft hole 4211, and polyvinylidene fluoride (PVDF) dissolved in a solvent (solvent) is supplied to the feeding port 43. As shown in FIG. 7, the polyvinylidene fluoride (PVDF) feeding route for the dissolved polyvinylidene fluoride (PVDF) up to the feeding port 43 was warmed to 20 ° C. or a little at room temperature by the dissolved polymer supply unit 44. It is heated to about 40 ° C. and then fed from the dissolved polymer supply unit 44 through the dissolved polymer supply pipe 441 by the gear pump 442 and the like, and further dissolved through the dissolved polymer supply unit 44 after the supply. The polyvinylidene fluoride (PVDF) thus prepared is supplied to the aforementioned dissolved polymer introduction tube 43.
The dissolved polymer introduction pipe 43 is provided with a warm water heat retaining part 45 so that the nozzle part 42 is maintained at 30 ° C. to 38 ° C., and is distributed to each nozzle part 42 by a water heater 452 with a heater pump 451. It is provided in the vessel 453 so as to maintain the temperature. As shown in FIG. 7, this arrangement is circulated so as to be connected in series by a pipe 455 from the hot water outlet 454 and return to the hot water return port 456.

Here, the reason why the hot water is used for maintaining the temperature of the dissolved polymer introduction tube 43 is that the temperature management is relatively easy and unlike the heater or the like, the environment is not dried.
In addition, the six nozzle portions 42 in one line in the vertical direction and the hot water main portion 45 connected to the nozzle portions 42 are integrated. The metal mesh) 51 is always moved in parallel in the range of 7.5 cm to 15 cm so that the thickness of the nanofiber laminate is uniform. Further, the distance from the nozzle part 42 to the plane holding grid (or wire net) 51 of the nanofiber collecting device 5 is about 165 cm, and the polymer material described later is sufficiently stretched, and the solvent such as toluene is used as the polymer material. It is trying to scatter from.
Note that polyvinylidene fluoride (PVDF) in Example 1 has a material concentration of 14 wt% using NMP as a solvent, as will be described later, in order to lower the viscosity. Further, the inner diameter of the discharge port 4212 is 0.1 mm to 0.2 mm, and is 0.15 mm in this embodiment. However, if it is 0.2 mm or more, it is difficult to obtain a nano-order thinness even if it is stretched. Good, but if it is less than 0.1 mm, the spinning speed will be slow.

[High-speed wind outlet 46]
As shown in FIGS. 7 and 8, the nozzle body 421 is provided with a ring-shaped high-speed air blowing passage 462 coaxially around the central shaft hole 4211 so as to wrap around the central shaft hole 4211. A ring-shaped high-speed air outlet 463 having a predetermined blowing angle is provided at the tip, and this high-speed air outlet 463 projects slightly from the outlet 463 by about X = 3 mm (2 to 5 mm) so that rectification occurs. I have to.
The function and adjustment of the protruding amount X are the same as those of the nozzle unit 22 described above. In addition, an air supply unit 48 connected to the other end of the high-speed wind blowing passage 462 is provided in the middle portion of the nanofiber blowing unit 415, and the air supply unit 48 has a room temperature of 20 ° C. or a slightly warm temperature of about 20-40 ° C. The air (air flow) is supplied by an air pump 481, and the polyvinylidene fluoride (PVDF) fiber spun from the discharge port 4212 is stretched so as to be pulled downstream so as to be wrapped by the high speed air flow of the high speed air outlet 463. The high-speed air outlet 463 having this predetermined blowing angle constitutes an extending air flow means.

Further, the nozzle portion 42 of the stretching air flow means mainly comprises a nozzle main body 421 and a nozzle support 422. As shown in the enlarged view in the vicinity of the discharge port 4212 in FIG. A central shaft hole 4211 through which molecules are ejected is provided, and a discharge port 4212 is provided at a distal end portion on the downstream side of the central shaft hole 4211. The material of the nozzle body 421 in the nozzle portion 42 of the present invention is optimally ceramic or ruby, and in this embodiment is ruby.
The nozzle inner diameter of the discharge port 4212 was changed from 0.13 mm to 0.18 mm. However, when it is 0.18 mm or more, it is difficult to form nano-unit fibrous adhesive, and when it is 0.13 mm or more, the nozzle inner diameter is melted. In this embodiment, the thickness is about 0.15 mm because the polymer is clogged. Further, in Patent Document 4 of the prior art, the nozzle inner diameter is set to 0.15 mm, but since the material is metal stainless steel, it has been found that the nozzle is immediately transformed into a thick fiber. It has been found that this is due to the expansion of the inner diameter of the stainless nozzle due to repeated loading and pressure. For this reason, when using a ruby (ceramic) that has excellent heat resistance and wear resistance and does not deform even at high temperatures, a high-quality polymer nanofiber laminate N5 could be produced even after continuous operation for a long time.

However, it is difficult to process ceramic and ruby, and it is difficult to fix the nozzle discharge port 4212 to the metal nozzle support 422 provided with screws or the like with screws or the like. Therefore, as shown in FIG. 8, a thick flange 4213 protruding outward is provided at the upstream end of the nozzle body 421, and the protrusion protruding inward at the downstream end of the corresponding inner hole 4221 of the nozzle support 422 is provided. A stop portion 4222 is provided, and the nozzle body 421 is inserted from the opening 4223 upstream of the inner hole 4221 of the nozzle support 422, and the flange portion 4213 is closely fitted and fixed to the locking portion 4222. With such a structure, the nozzle main body 421 is not detached from the nozzle support 422 even when the molten polymer is inserted at a high pressure downstream. In this case, the inner diameter of the inner hole 4221 is larger than the outer diameter of the nozzle body 421 and the outer diameter of the flange portion 4213, and the inner diameter of the tip locking portion 4222 of the nozzle support 422 is smaller than the outer diameter of the nozzle body 421. It is necessary to make it smaller than the outer diameter of the portion 4213.
The dissolved polymer introduction tube 43 communicating with the nozzle portion 42 is supplied with a resin dissolved by an appropriate means.
If the nozzle body 421 is moved while maintaining the same distance in the horizontal direction with respect to N3 in which the second fibrous polymer adhesive is sprayed on the base N1 as necessary, the number of the nozzle bodies 421 is reduced. Can be reduced.
Spacer portions (not shown) for maintaining a passage gap are provided at appropriate positions between the outer peripheral portion 431 of the central shaft hole 4211 and the outer peripheral portion 4224 on the discharge port 4212 side and the inner peripheral wall of the high-speed air blowing passage 462. Thus, the high-speed air blowing passage 462 is formed.

The stretching air flow means will be further described. Since the polyvinylidene fluoride (PVDF) fiber is further drawn with a high-speed air flow, the blowing angle of the ring-shaped high-speed air blowing outlet 463 (the combined angle on the left and right with respect to the axis of the central shaft hole 4211). However, as a result of the experiment, the angle of about 30 ° to 60 °, that is, the direction of the high-speed air flow at the high-speed air outlet 463 is 15 ° to 30 ° with respect to the central axis of the discharge port 4212 of the central axis. The angle range is preferably 30 ° (center axis and angle 15 °) or less, the contact force with polyvinylidene fluoride (PVDF) is small and the stretching action is small, and the angle is 60 ° (center axis and angle 30 °) or more. However, since no negative pressure is generated by contact, the stretching action is still small. In Example 1, the stretching action was effectively performed by setting the angle to 38 ° (angle 19 ° to the central axis).
As described above, unless the airflow from the high-speed air outlet 463 hits the appropriately spun polyvinylidene fluoride (PVDF) fiber, it ends with microfibers on the order of μ and does not become nanofibers.
In order to efficiently draw polyvinylidene fluoride (PVDF) fiber, it is also important to make the viscosity lower than that of a solvent such as NMP in order to obtain a dissolved polyvinylidene fluoride (PVDF) fiber. It must be possible to discharge the dissolved polyvinylidene fluoride (PVDF) from the 0.15 mm outlet 4212.

Further, the drawing air flow means needs to be drawn with the high-speed jet air J after spinning from the discharge port 4212. More importantly, the drawing air drawing means draws a solvent such as NMP contained in the polyvinylidene fluoride (PVDF) fiber while drawing. Therefore, the high-speed air outlet 463 slightly protrudes from the discharge port 4212 of the spinning nozzle portion 42 by about X1 = 4 mm (2 to 4 mm), and the polyfluorination spun from the discharge port 4212 It is comprised so that the vaporization of the solvent of a vinylidene (PVDF) fiber or the drying of a polyvinylidene fluoride (PVDF) fiber may be accelerated | stimulated.
When the predetermined distance X1 in the flow direction between the high-speed air outlet 461 and the discharge port 4212 is a protrusion of 5 mm or more, the stretching action of the PVDF fiber due to the high-speed air is weakened, and when it is 1 mm or less, the vaporization of the solvent is weakened. The fiber itself curls and adheres, and it is difficult to form beautiful PVDF nanofibers. Thus, it is important to achieve both the stretching of the polyvinylidene fluoride (PVDF) fiber and the rapid removal of the solvent.
In addition, as shown in FIG. 7, it is formed in a gap between the air introduction part frame 472 and the dissolved polymer introduction pipe 43, and is a cylinder having a diameter of about 2 cm in the downstream direction of the injection air path forming cap 47 and having a length of about 7 cm. The nozzle wind tunnel 49 (hood) is attached to the male screw portion 471 of the blast air path forming cap 47 with an attaching female screw 471.
Since the nozzle wind tunnel 49 (FIG. 6) is arranged immediately after the discharge port 4212 of the nozzle portion 42, the spun dissolved polymer is stretched linearly, the stretching time of the resin is extended, and the fiber diameter is extremely fine. And can be prevented from interfering with high-speed winds discharged from other nearest nozzles. As a result, a uniform nanofiber laminate can be obtained. Then, when the solvent such as NMP is vaporized and removed from the polyvinylidene fluoride (PVDF) fiber, the drawing ends and the nanofiber collecting part of the [nanofiber collecting step E2] of the downstream nanofiber laminate forming step E Collected at 5.

[Nanofiber collection process E2]
As shown in FIG. 1, the nanofibers blown off from the nozzle portion 42 and the air high-speed air blowing nozzle portion 461 are collected by the downstream nanofiber collecting device 5.
This nanofiber collecting device 5 is provided with a plane holding grid (or wire net) 51 having fine through holes facing the nanofiber N4 to be sprayed, and a suction duct 52 is provided on the back side to which the nanofiber N4 is sprayed. It has been.
A feed roller 13c is provided upstream at both ends of the above-described plane holding grid (or wire mesh) 51, and a feed roller 13d is provided downstream, and the drawn substrate N1 such as a nonwoven fabric is placed on the plane holding grid (or wire mesh). 51, the laminated body of nanofibers N4 is moved while being placed on the upper surfaces of the base materials N1, N2, and N3, and the following [Deodorant Attaching Step F], product nanofibers N5 sprayed with a deodorant are attached. It is sent to the [Nanofiber winding process G] to be wound.

[Deodorant attachment process F]
Titanium oxide is attached to the nanofiber laminate while the second fibrous polymer adhesive N3 of the nanofiber laminate produced in the nanofiber collecting step E2 is not completely cured. Conventionally, zinc oxide has been kneaded into polyvinylidene fluoride (PVDF), but since it is attached near the surface of the fiber, it also has a deodorizing effect. In addition, when titanium oxide near the nanofiber surface is irradiated with light, active oxygen such as OH radicals is generated, and this OH radical has a much stronger oxidizing power than chlorine, hypochlorous acid, hydrogen peroxide, ozone, etc. It can be understood that chemical substances that are difficult to be decomposed by its oxidizing power can be safely decomposed, can be expected to have a deodorizing effect than conventional zinc oxide, and are attached and fixed to the surface of titanium oxide. The odor effect is increased.
The deodorant attachment portion 6 will be described with reference to FIG. 9. Compressed air 65 is fed into a pressurized tank 63 storing a deodorant solution obtained by dissolving titanium oxide with toluene or the like, and sprayed from the pressurized tank 63. The titanium oxide solution is sprayed from the deodorant spray 61 to the nanofiber laminate N4 through the agent supply pipe 64.
Specifically, this deodorant liquid has the following composition ratio.
Deodorant (odour-absorbing agent): Titanium oxide 6.6 wt /% (% to total weight: w / w%) N-methylpyrrolidone (NMP): 75.4 wt /% Toluene : 4.7 wt /%
The deodorant spray 61 is uniformly sprayed with a titanium oxide solution on the surface of the nanofiber laminate N4 by the spray driving device 62, and is transferred to the next nanofiber winding step.

[Nanofiber laminate winding process G]
The product nanofiber laminate N5 having titanium oxide dispersed on the surface travels a sufficiently long distance (about 5 m) from the second polymer resin spraying portion 21b to the take-up rod 71 to sufficiently cure the second polymer resin. Thus, the take-up rod 71 of the nanofiber laminate N4 is taken up by driving the feed roller 72. (Figure 1)

[Nanofiber laminate product N5]
A nanofiber laminate in a state as shown in FIG. 14 (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3) of the micrograph was produced under the following conditions.
Setting conditions (Example)
material:
(1) Main agent: Kureha Co., Ltd. Polyvinylidene fluoride (PVDF) 13.3 wt /% (% to total weight: w / w%) Solvent (solvent): Nihon Refine Co., Ltd. solution discharge pressure: 0.15 MPa
High-speed air blowing angle 38 °
High-speed air pressure: 0.26 MPa
High-speed air flow: 34L / min
Fiber diameter: 200-500 nm

  In this example, polyvinylidene fluoride (PVDF) was used as the material for the nanofibers of the polymer fiber, and N-methylpyrrolidone (NMP) was used as the solvent. As other combinations of polymer and solvent, nylon (manufactured by Ube: 1022B) and formic acid as solvent (solvent), as well as polyetherimide (PEI) and solvent as DMF and dimethylacetamide (DMAc) are the same. In addition, polyacrylonitrile (PolyAcryloNitrile, PAN), polyether sulfone (Poly Ether Sulphone, PES) and dimethylacetamide (DMAc) or DMF (dimethylformamide), chitosan and acetic acid or citric acid and other weak acids A combination of acrylic (PolyMethyl MethAcrylate, PMMA) and methanol, polylactic acid and chloroform, etc. It is possible as a production of over.

[Characteristics of Nanofiber Laminate N4 of this Example for Thin Film Deodorizing and Shading Member for Building Materials]
The configuration of the filter using the nanofibers of this example is as follows.
(1) Substrate N1: Polypropylene (PP): 0.25 mm diameter monofilament 18 mesh, thickness: 0.48 mm, weight: 80 g / m ²
(2) 1st polymer adhesive N2: Polyurethane hot melt adhesive (quick drying moisture curing type)
Fiber having a diameter of 10 nm to 100 μm: Weight 3 g / mm ³
(3) Second polymer adhesive N3: polyurethane hot melt adhesive (moisture-curing type)
Fiber with a diameter of 500 nm to 10 μm: Weight 2 g / mm ³
(4) Nanofiber N4: Polyvinylidene fluoride (PVDF) 200 to 50 nm diameter fiber: Weight 0.8 g / mm ³
(5) Product thickness (base material N1 + first polymer adhesive N2 + second polymer adhesive N3 + nanofiber N4): 0.5 mm

The fiber diameter of the substrate N1 is a 0.25 mm monofilament, but if it is too thin, the strength is insufficient, and if it is too thick, the thickness of the product increases and the shading rate increases, resulting in darkness. The diameter of the filament is preferably from 0.1 to 0.5 mm, and the coarse mesh of the mono- or multifilament woven or knitted fabric is preferably a mesh of 15 to 30 mesh.
The first polymer adhesive N2 is polyurethane, but may be an olefin adhesive, and the fiber diameter is 10 nm to 100 μm, but the weight is 1 to 5 g / mm ^3. N2 should have a relatively fast curing and drying speed of several seconds (sec) in order to form a mesh.
Although the second polymer adhesive N3 and polyurethane were used, an olefin-based adhesive may be used, and the fiber diameter may be 500 nm to 10 μm, but the weight may be 1 to 5 g / mm ³ , and the second polymer adhesive N3 In order to make the bonding time as long as possible, it is preferable that the curing / drying speed be about 1 hour (sec) or longer and relatively slow.
Moreover, although titanium oxide was dissolved in toluene in nanofiber N4 and dispersed on the surface of polyvinylidene fluoride (PVDF), as described above, the material of the nanofiber of the polymer fiber may be nylon or the like, but titanium oxide was dissolved. It is preferable that the nanofiber laminate N4 can be sprayed and fixed easily by spraying toluene and has excellent weather resistance. Further, although the fiber diameter is 200 nm to 1 μm and the weight is 0.8 g / mm ³ , it is preferably a nanofiber laminate having a low light shielding property and a high collection rate of pollen and the like.

Since it is the above structure, since it is a very thin shielding member of about 1 μm compared with 0.3 mm of the base material N1 having a thickness, it is adhered to the base material N1, so that it is sufficient as a whole. Has strength.
The actual final product thickness (base material N1 + first polymer adhesive N2 + second polymer adhesive N3 + nanofiber N5 dispersed and fixed with titanium oxide) is also 0.5 mm, and the thickness of the base material N1 is 0.48 mm. Compared to the diameter, it is only increased to 0.12 mm, it is extremely thin, and the light shielding rate can be extremely low.
In addition, the UV shading rate is 58% (spectrophotometer, all-wavelength average method using a uniform evaluation method for processing effects of UV-cut materials (Japan Chemical Fibers Association), bandpass filter installed between integrating sphere and detector). Yes, the transmittance is 38.9% at a wavelength of 305 nm, and the transmittance is 44.1% at a wavelength of 360 nm. The shading rate is 64.62% (illuminance after 3538 lx wearing) (JISL1055A method: illuminance before wearing test piece: 10000 lx. Test piece light source side: coated surface), and this value is the thinnest translucency of commercially available curtains. Even if the rate is 55 to 70%, it can be seen that the outdoor light is taken in sufficiently.

The air permeability is also 423.8cm ³ / cm ² · s, which is sufficient compared to the filter effect, but the pollen collection (filtering) efficiency of the present invention is 89.1%. It is clear that it can be used as a building material that prevents pollen and fine insects from entering.
That is, with the test system sucked at a constant air flow rate, the test powder (pollen substitute particles) sized by the sizing device is dropped from above the filter section at a constant speed. The mass of particles trapped in the filter part and the mass of particles passed through the filter part were measured, and the following formula or the collection (filtration) efficiency was calculated.
Pollen particle trapping (filtration) efficiency% = mass of particles trapped in the filter (mg) / (particle mass trapped in the filter (mg) + mass of particles passing through the filter (mg)) Test conditions Test powder Body (pollen substitute particles): Ishimatsuko (APPIE standard powder) Test fluid: 28.3 L / min
Large amount of test powder: 75 ± 5mg
Test powder speed: 20 ± 5 mg / min
Temperature and humidity of test room: 20 ± 5 ° C, 50 ± 10% RH

The deodorizing property that is a feature of this example (the present invention) will be described.
First, the ammonia gas removal performance evaluation test was carried out by applying the method defined by the SEK mark fiber product certification standards ((one company) Fiber Evaluation Technology Council) to the Kaken Test Center. However, the sample volume is “90 pieces of 10 cm × 10 cm + 10 pieces of 10 cm × 3 cm”, and the type of bag used is Smart Bag PA (manufactured by GL Sciences). Test conditions for ammonia gas removal performance evaluation test Same ammonia A state where the sample amount of the present example was present in an atmosphere of a predetermined volume (200 ml) with an initial gas concentration of 100 ppm, and a state where there was nothing as a conventional example and a comparative example (blank test) were left for 2 hours. The following table compares the gas concentrations.
Ammonia gas removal performance evaluation test Test sample Sample initial concentration (ppm) Gas concentration (ppm) after 2 hours Reduction rate (%)
Example 100 1.0 ≧ 99
Conventional example (kneaded with zinc oxide)
100 15 81
Comparative example (blank) 100 80 ----
As described above, the ammonia gas concentration is reduced by 99% against the empty state, which is a remarkable effect compared to the 81% reduction of the conventional nanofiber laminate containing zinc oxide. I know that there is.

Next, a hydrogen sulfide gas removal performance evaluation test was carried out. The method defined by the SEK Mark Textile Product Certification Standard ((One Company) Textile Evaluation Technology Council) was applied mutatis mutandis to the Kaken Test Center. Carried out. However, the sample size is “10 cm x 10 cm 90 sheets + 10 cm x 3 cm 10 sheets”, the type of bag used is Smart Bag PA (manufactured by GL Sciences), and the test conditions for the hydrogen sulfide gas removal performance evaluation test are the same. A state in which the sample amount of the present example was present in an atmosphere of a predetermined capacity (200 ml) with an initial concentration of hydrogen sulfide gas of 4.0 ppm and a state in which there was nothing as a comparative example (blank test) were left for 2 hours. The following table compares the gas concentrations.
Ammonia gas removal performance evaluation test Test sample Sample initial concentration (ppm) Gas concentration (ppm) after 2 hours Reduction rate (%)
Example 4.0 ≦ 0.05 ≧ 99
Comparative example (blank) 4.0 4.0 ----
As described above, it can be seen that the concentration of hydrogen sulfide gas is reduced by 99% in the empty state where there is nothing, and there is a remarkable effect.

Thus, the thin film deodorization shielding member of the embodiment of the present invention has a sufficient deodorizing effect, sufficient air permeability, lowers the light shielding rate, and increases the collection efficiency of pollen particles. it can. In addition, since the nanofiber material is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is also a resin that is resistant to radiation, so it is also suitable as a building material for screen doors and agricultural houses to be deployed outdoors. Cleaning is also easy.
Here, titanium oxide was dissolved in toluene and dispersed onto polyvinylidene fluoride (PVDF) as a material of the nanofiber laminate N4. The polyvinylidene fluoride (PVDF) was one of the thermoplastics and had a melting point. Is a high-strength resin having a temperature in the range of 134 to 169 ° C. The heat-resistant temperature that can be used regularly is around 150 ° C, a material with good thermal stability, and titanium oxide dissolved in toluene. It is also familiar, yet has good chemical resistance, excellent processability, flame resistance, and less smoke when burned. Good electrical properties, excellent ferroelectricity and piezoelectricity, especially excellent resistance to weathering and radiation-resistant resin, so it is also suitable as a building material for screen doors and agricultural houses to be deployed outdoors. And can be easily cleaned.

Thus, the thin film deodorization shielding member of the embodiment of the present invention has a sufficient deodorizing effect, sufficient air permeability, lowers the light shielding rate, and increases the collection efficiency of pollen particles. it can. In addition, since the nanofiber material is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is also a resin that is resistant to radiation, so it is also suitable as a building material for screen doors and agricultural houses to be deployed outdoors. Cleaning is also easy.
Needless to say, the present invention is not limited to the above-described embodiments as long as the features of the present invention are not impaired.

A ·· Base material feeding step, B ·· Reticulated reinforcing fiber forming step, C ·· First polymer adhesive cooling step, D ·· Second polymer adhesive spraying step, E ·· Nanofiber generation step, F・ ・ Deodorant attachment process, G ・ ・ Nanofiber laminate winding process, H ・ ・ High-speed heated air, J ・ ・ High-speed jet air,
N1 ... Base material, N2 ... First fiber polymer adhesive (base material), N3 ... Second fiber polymer adhesive (base material), N4 ... Nanofiber laminate, N5 ... Product Nanofiber laminates,
1 .... Base material supply section, 11 .... Take-up rod, 12 .... Feed roller,
13 (a, b, c, d) ... guide rollers, 14 ... tension adjusting mechanism,
2 .. Reticulated reinforcing fiber forming part,
21 .. First polymer resin spraying part,
(21b ··· Second polymer resin spraying portion) 22 · · Nozzle portion,
221 .. Nozzle body, 2211...
2212 ..Discharge port, 2213 ..Saddle, 222 ..Nozzle support,
2221 .. Inner hole, 2222 .. Locking part, 2223 .. Opening,
2224 .. Outer periphery,
23 .. Molten resin introduction pipe, 231 .. Outer peripheral part, 232 .. Hot air introduction groove, 234 .. Molten resin introduction path, 24 .. Adhesive supply part, 241 .. Adhesive supply pipe,
242..Supply pump 25..Adhesive collecting part,
26 .. Hot air blowing part, 261 .. Hot air blowing nozzle part,
262 ... High-speed hot air outlet passage 263 High-speed air outlet
H.264 ... Heater
27 .. Heated air passage forming cap, 271 .. Male screw part, 272 .. Heated air introduction part frame, 273 .. Washer for fine adjustment,
28 .... Air pump, 281 ... Hot air generator, 282 ... Air supply pipe,
29 .. Nozzle wind tunnel 3 .. Cooling device 31.. Cooling plate 32.. Heat insulation plate 33.
34 ... Peltier device, 341 ... N-type thermoelectric semiconductor,
342 .. P-type thermoelectric semiconductor, 343, 343u, 343d .. Metal electrode,
344 .. Insulating material 345 .. DC power supply 4.. Nanofiber spinning nozzle 41.. Nanofiber spraying part
42 .. Nozzle part, 421 .. Nozzle body, 4211...
4212 ··· discharge port, 4213 ·· collar, 422 · · nozzle support,
4221 ... Inner hole, 4222 ... Locking part, 4223 ... Opening,
4224 .. Outer periphery,
43 .. Dissolving polymer introduction pipe, 431 .. Outer peripheral part, 432 .. Injection air introduction groove,
44 .. Dissolving polymer supply section, 441 .. Dissolving polymer supply pipe,
442 ... Gear pump,
45 .. Warm water warming part, 451 ... Heater pump, 452 ... Water heater,
453 ... Distributor 454 Hot water outlet 455 Piping
456 ... Warm water return port,
457 .. Left and right traverse mechanism (nozzle part 42, warm water heat retaining part 45),
46 ··· High-speed air blowing part, 461 ··· High-speed air blowing nozzle part,
462 ... High-speed wind outlet passage, 463 ... High-speed wind outlet,
47..High-speed air passage forming cap, 471..Male thread part,
472 .. Air introduction part frame,
48 .... Air supply part, 481 ... Air pump, 49 ... Nozzle wind tunnel,
5 .... Nanofiber collecting device, 51 .... Plane holding grid (or wire mesh),
52 .. Suction duct,
6. Deodorant attachment part, 61. Deodorant spray, 62. Spray drive,
63 ... Pressurized tank, 64 ... Spray agent supply pipe, 65 ... Compressed air,
7 ··· Nanofiber laminate winding part, 71 · · Winding rod,
72. Feed roller

Claims (10)

A first fiber-like polymer adhesive is sprayed onto the base material by a first adhesive spray on a base material having a coarse or coarse strength with a mono or multifilament knitted fabric, and immediately after passing through a cooling device, the first fiber is passed through. The polymer adhesive is rapidly cured to form a finer mesh in the base of the base material to form a reinforcing base,
A second fiber-like polymer adhesive having a curing time slower than that of the first fiber-like polymer adhesive is applied to the base material and the reinforcing base material with a fiber diameter of 500 nm to 10 μm by an adhesive spray. Thinly spray the net formed of molecular adhesive to shrink the gap so as not to close it,
A nanofiber of a polymer material having a long molecular arrangement is sprayed and laminated on the second fibrous polymer adhesive thinly sprayed by a nanofiber spray, and the base material, the reinforcing base material, and the nanofiber are laminated. Glue,
The method for producing a nanofiber laminate, wherein the second fibrous polymer adhesive has air permeability and light permeability so as not to block gaps between the nanofibers.   The method for producing a nanofiber laminate according to claim 1, wherein the nozzle of the nanofiber spray is ceramic or ruby.   3. The method for producing a nanofiber laminate selected from claims 1 to 2, wherein titanium oxide is dispersed as a deodorant in the nanofiber laminate.   4. The titanium oxide is attached by spraying 2 to 20% by weight of titanium oxide as a deodorizing material on the polyvinylidene fluoride with the polymer fiber as polyvinylidene fluoride (PVDF). A method for producing a nanofiber laminate as described in 1.   The mono- or multi-filament is 0.1 to 0.5 mm diameter polypropylene (PP), and the coarse texture of the mono- or multi-filament woven or knitted fabric is 15 to 30 mesh. A method of laminating nanofibers selected from the description.   The first fiber-like polymer adhesive is formed by spraying a fiber having a fiber-like diameter of 10 μm to 100 μm on a substrate and passing through a gap of a cooling plate of a cooling device disposed immediately downstream. The method for producing a nanofiber laminate selected from claims 1 to 5, wherein the polymer adhesive is rapidly cured.   The said cooling device is comprised with the thermocouple, and the surface temperature of the cooling plate was -10 degreeC to -20 degreeC, The manufacturing method of the nanofiber lamination | stacking of Claim 6 characterized by the above-mentioned.   The first fiber-like polymer adhesive forms a network and has an adhesive property to the base material, the fiber-like second polymer adhesive, and the nanofiber so as not to form a film. A method for producing a nanofiber laminate selected from claims 1 to 7.   Before the sprayed second fibrous polymer adhesive is cured, the nanofiber laminate produced from the nanofiber production part of the polymer fiber is sprayed, and further, titanium oxide is dispersed and wound up. A method for producing a nanofiber laminate selected from claims 1 to 8.   A first fiber-like polymer adhesive is sprayed onto the base material by a first adhesive spray on a base material having a coarse or coarse strength with a mono or multifilament knitted fabric, and immediately after passing through a cooling device, the first fiber is passed through. The solid polymer adhesive is rapidly cured to form a finer spider web to form a reinforcing base, and the reinforcing base has a solidification time from the first fibrous polymer adhesive. The slow second fibrous polymer adhesive is sprayed thinly so as not to block the gaps in the mesh formed with the fiber-shaped first polymer adhesive having a fiber diameter of 500 nm to 10 μm. The nanofibers of polymer fibers are sprayed and laminated on the second fibrous polymer adhesive to bond the reinforcing substrate and the nanofibers, and the second fibrous polymer adhesive is bonded to the nanofiber. Thin deodorizing shielding member for building materials not block even gap fiber characterized by using the nanofiber laminate having a permeability and light transmittance.