JP6943413B2 - Manufacturing method of nanofiber laminate - Google Patents

Description

The present invention is a method for manufacturing a nanofiber laminate and a thin film deodorant shielding member for building materials using the same, and in particular, a device for manufacturing a thin film deodorant shielding member for building materials, which shields the outside air from the room. Manufacture of nanofiber laminates that are used for breathable screen doors and agricultural houses to prevent the ingress of pollen and fine insects, absorb the offensive odor of the outside air, allow air to enter and exit, and have light transmission. A method and a thin film deodorant shielding member for building materials using the method.

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

In addition to the electro-spinning method described above, Non-Patent Document 1 also describes a Kaishima composite spinning method and a low-viscosity molten polymer as a method for producing micro-orders, which are conventional synthetic fibers that do not use high-pressure electrodes. It is disclosed that a melt blow spinning method in which the polymer is blown off and a flash spinning method in which the polymer solution is rapidly expanded to solidify and become fibrous while blowing off the polymer are being developed. As a method for producing ultrafine fibers only by melting, the above-mentioned Non-Patent Document 1 includes a polymer blend spinning method as a method of dissolving in a solution and spinning, which is a blend of two kinds of polymers and the fibers. It is an ultrafine spinning method in which sea polymer is eluted after conversion, and μm is the limit.
Therefore, as shown in Patent Document 2, the present inventors have succeeded in producing nanofibers by dissolving a polymer in a solvent to reduce the viscosity, and further blowing and stretching the polymer together with jet air from a nozzle having an ultrafine diameter. Utilizing this, a thin film deodorant shielding member that captures fine particulate matter PM2.5 suspended in the atmosphere that deposits on the respiratory system and affects health is manufactured.

By the way, there is a screen door to prevent mosquitoes, dead insects, dust, etc. from entering the room while maintaining breathability, but recently it is removable to prevent extremely minute harmful substances such as pollen from entering the room. Screen doors with various filter covers have been developed. Further, also in an agricultural house, an insect repellent net which is breathable but does not allow minute insects to enter has been developed as shown in Patent Document 3. Further, as shown in Patent Document 4, a screen door using a non-woven fabric mixed with titanium oxide to deodorize an offensive odor has already been proposed. However, it is not a manufacturing method for inexpensively manufacturing a thin film deodorant shielding member that captures fine particulate matter PM2.5.

Japanese Unexamined Patent Publication No. 2011-127234 Japanese Unexamined Patent Publication No. 2014-144579 Utility Model Registration No. 3034455 Japanese Unexamined Patent Publication No. 2000-217446

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

However, since the non-woven fabric of the screen door filter and the shielding member of the agricultural house described above is a fiber of micro order at most, it must be laminated thickly in order to capture and shield the fine particulate matter PM2.5, and still completely. Could not shield pollen and the like.
In addition, since the non-woven fabric is thick, the degree of shading is large, the room becomes dark, and the material cost is high.
On the other hand, filters using nanofibers have been developed as materials such as masks that shield pollen, etc., but because the nanofibers themselves are expensive and the nanofibers are sandwiched between the base materials and held, they can be fixed. There were inconveniences such as problems, and there were problems such as lack of strength.
The subject of the present invention has been made in view of such problems, and a shielding member made of a nanofiber non-woven fabric, which has breathability and captures fine particulate matter PM2.5, has sufficient strength. It is intended to provide a manufacturing method that has sufficient deodorizing effect and is inexpensive to manufacture.
Further, the thin film deodorant shielding member for building materials in which nanofibers of Patent Document 4 are laminated captures the fine particulate matter PM2.5, but the adhesion durability between the nanofibers and the first and second fibrous polymer adhesives. There is also a problem of durability that the nanofiber laminate peels off from the base material when used outdoors for a long period of time, and there is also a problem of durability of the deodorizing effect. It is intended to provide a manufacturing method that overcomes the points.

In order to solve the above problems, the invention of claim 1, PP (polypropylene), polyethylene (PE), polyester (PET), coarse eyes woven or knitted fabric mono or multifilament selected from polyphenylene sulfide (PPS) The first polymer adhesive of a moisture-curable polyurethane hot-melt adhesive is sprayed onto the base material in a fiber form by the first adhesive spray, and placed immediately after the downstream. The temperature of the cooling plate in the cooling device is changed from -10 ° C to -20 ° C and passed through the gap to cure the first polymer adhesive to form a finer mesh in the mesh of the base material to form a reinforcing base material.
A fiber having a diameter of 500 nm to 10 μm is applied to the base material and the reinforcing base material by spraying a second polymer adhesive, which is a moisture-curable polyurethane hot-melt adhesive having a curing time slower than that of the first polymer adhesive. As a form, the second polymer adhesive is shrunk by spraying thinly on the net formed of the first polymer adhesive so as not to close the gap.
Immediately after that, polyvinylidene fluoride (PVDF), nylon, polyetherimide (PEI), polyacrylonitrile, and polyether monkey, which are polymer materials having a long molecular arrangement on the second polymer adhesive sprayed thinly in the form of fibers. Nanofibers selected from phon and acrylic are sprayed and laminated by nanofiber spray so that the second polymer adhesive has air permeability and light transmission so as not to block the gaps between the nanofibers. The nanofibers are characterized in that the base material, the reinforcing base material, and the nanofibers are adhered to each other, and then a deodorant is sprayed on the surface of the nanofibers while the nanofibers are in a highly adhesive state before being cured. This is a method for manufacturing a laminate.

The invention of claim 2 is characterized in that, in the method for producing a nanofiber laminate according to claim 1, titanium oxide is sprayed on the nanofiber laminate as the deodorant.
The invention of claim 3 uses polyvinylidene fluoride (PVDF) as the polymer material in the method for producing a nanofiber laminate according to claim 2, and the titanium oxide to be sprayed is based on polyvinylidene fluoride. It is characterized in that 2 to 20% by weight of titanium oxide is sprayed and adhered as a deodorant.
According to a fourth aspect of the present invention, in the method for producing a nanofiber laminate selected from the first to third aspects, the mono or multifilament is polypropylene (PP) having a diameter of 0.1 to 0.5 mm, and the mono. Alternatively, the coarse mesh of the woven or knitted fabric made of multifilament is 15 to 30 mesh.
The invention of claim 5 is the method for producing a nanofiber laminate according to claim 1.
The cooling apparatus is characterized in the configuration of Reruko by a thermocouple.

According to the method for producing nanofiber laminates of the present invention and the thin film deodorant shielding member for building materials using the same, the nanofibers have sufficient strength even though they are thin shielding members, and the durability is increased. There is little peeling between the fiber laminate and the base material, it has sufficient breathability, it has a low light-shielding rate, it prevents pollen particles and fine insects from entering, it increases the collection efficiency, and it has a strange odor such as ammonia gas. Can be efficiently decomposed, and its deodorizing effect can be maintained for a long time.
In addition, if the nanofiber material is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is 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. , Easy to clean.
Furthermore, since the nozzles for spraying adhesives and nanofibers are made of ceramic or ruby, the central discharge port is heat resistant, durable and has little deformation, and even if high-temperature heated polymer fibers are spun for a long time, nanofibers. There is no deformation, and a uniform nanofiber diameter can be maintained.
Furthermore, in the thin film deodorant shielding member for building materials in which nanofibers are laminated, even if it is thin, it has sufficient strength and sufficient air permeability, and the light shielding rate is lowered to prevent the invasion of pollen particles and fine insects. It is highly efficient, has sufficient strength, efficiently decomposes offensive odors such as ammonia gas, and can be mass-produced at low cost.

Schematic diagram of the overall concept of the method for producing a nanofiber laminate according to an embodiment of the present invention. Cross-sectional view of the first (second) polymer adhesive nozzle of FIG. Enlarged view of the nozzle of FIG. 2 and the injection air blowing nozzle at the tip thereof, FIG. 2, a cross-sectional view of the molten resin introduction pipe 23 along the X1-X1 line of FIG. Sectional view of the cooling device of FIG. Explanatory drawing of the perche device of FIG. 5, Explanatory partial cross-sectional view of the nanofiber generation step E1 of FIG. Enlarged view of the nozzle of FIG. 7 and the high-speed wind blowing nozzle at the tip thereof, Explanatory drawing of the deodorant spraying device of FIG. A micrograph of only the base material N1 in the examples of the present invention, A micrograph of the base material and the reinforcing base material N2 obtained by spraying the first polymer adhesive N2 on the base material N1 and passing it through an operating cooling device to the thing of FIG. 10 in the embodiment of the present invention. FIG. 10, a micrograph of the base material and the reinforcing base material N2 when the first polymer adhesive N2 is sprayed onto the base material N1 and the cooling device is not operated. A micrograph of FIG. 11A of the embodiment in the present invention, in which the base material N1 and the first polymer adhesive N2 are sprayed, and the second polymer adhesive N3 is sprayed. A micrograph from the nanofiber side in which nanofibers N4 in which the second polymer adhesive N3 is sprayed on the base material N1 and the first polymer adhesive N2 are laminated on the thing of FIG. 12 of the embodiment of the present invention. figure, A micrograph of a state in which nanofibers N4 are laminated by spraying a second polymer adhesive N3 on a base material N1 and a first polymer adhesive N2 in the state of FIG. 13 of an embodiment of the present invention, and a deodorant is sprayed and fixed. figure.

The features of the present invention are a method for manufacturing 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 deodorant shielding member such as a filter for a building material using the same. Specifically, a first adhesive material having a fiber diameter of 10 to 100 μm, which is thicker than nanofibers, is sprayed onto the base material, which is a mono or multifilament woven or knitted material and has coarse grain strength. The finer eyes are made of spider web-like fibers to improve the adhesiveness and the strength of the nanofibers is reinforced. A thin spray is applied to the base material reinforced with the material so as not to block the gap, and nanofibers are laminated on the second adhesive to bond the base material and the nanofibers. The second adhesive, which is quick-drying and has a strong adhesive force but requires a long time to cure, is characterized by being sprayed to increase the adhesive strength of the first adhesive and immediately after being cooled by a cooling device. After spraying nanofibers, it is run for a long distance and then wound up.
Hereinafter, the method for producing the nanofiber laminate of the present invention and the drawings of suitable examples of the thin film deodorant shielding member for building materials using the same will be described.

A method for manufacturing a nanofiber laminate according to Example 1 of the present invention and a thin film deodorant shielding member for a building material using the same will be described with reference to a conceptual explanatory view showing an overall outline of FIG.
As shown in FIG. 1, the outline of the nanofiber laminated manufacturing apparatus is in the following process order. First, the first step is a step of feeding out the base material N1 woven by monofilament [base material feeding step A], and the next step is a step of spraying the first polymer adhesive N2 on the fed out base material and using the first adhesive fiber of the spider. A step of forming a nest-shaped or zigzag-shaped net portion and adhering to the base material to reinforce the base material [net-like reinforcing fiber forming step B], spraying the first fiber-like polymer adhesive N2 on 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 adhering a second adhesive nanofiber to a reinforced base material to form an adhesive portion [first 2 Polymer adhesive spraying step D], nanofiber N4 spraying on the polymer adhesive N3 [nanofiber generation step E], deodorant spraying on the nanofibers [deodorant attachment step F], It is composed of a step of winding up the product nanofiber N5 sprayed with a deodorant [nanofiber laminate winding step G]. Therefore, each of the above-mentioned steps will be described in detail in sequence.

[Base material feeding step A]
The single body of the base material N1 of this example is as shown in FIG. 10 of a micrograph, and is woven with a 0.25 mm diameter PP (polypropylene) monofilament used for a normal screen door, and is 1 inch (25.4 mm). ) It is an 18 mesh net (Dio Kasei Co., Ltd. insect repellent net (product number mesh 18)) with 18 squares x 18 squares in the corner, the thickness is 0.48 mm, and the weight is 80 g / m2. The base material is strong enough to be used as a building material for screen doors and the like. In addition to the above PP (polypropylene), polyethylene (PE), polyester (PET), polyphenylene sulfide (PPS), or the like may be used as the base material N1, and the diameter of the mono or multifilament is 0.1 to 1. The diameter is 0.5 mm, and the coarse mesh of the woven or knitted fabric made of this mono or multifilament may be 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 unit 1 in the region [A], and is pressure-welded downward from the take-up rod 11. The feed roller 12 is sent to the next step [reticulated reinforcing fiber forming step B] via the plurality of guide rollers 13 and the tension adjusting mechanism 14.

[Reinforcing fiber forming step B]
The reticulated reinforcing fiber forming portion 2 of the reticulated reinforcing fiber forming step B sprays the first polymer adhesive onto the sent base material N1 and crosslinks it with spider web-shaped or zigzag-shaped fibers to form a mesh. In addition to preventing the woven mesh 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. , Prevents the nanofiber layer from breaking.
This state is as shown in FIG. 12 of the microphotograph, and the first nanofiber-like polymer adhesive has an average thickness of 10 to 100 μm in the space portion of the square mesh on the base material N1, which is thicker than the nanofiber N4. A finer mesh is formed by bridging and stretching spider web-shaped or zigzag-shaped fibers with fibers (N2), and the nanofiber layer N4 in the subsequent process is applied to the second nanofiber-like polymer adhesive in this fine mesh. The strength of the nanofiber laminate is improved by adhering (N3) with the adhesive of.

This first fibrous polymer adhesive N2 is a cross-linking and reinforcing adhesive (manufactured by KLEIBERIT PUR Reactive Hot Melt (Product No. 703.5)) and extends like a spider web. It has properties and is convenient for forming a fine crosslinked network. Further, since the adhesive of this first polymer adhesive does not need to be heated and gradually cures (several seconds) at room temperature, the base material N1 And nanofiber N4 are not altered.
However, the first fibrous polymer adhesive N2 is not completely cured even if it dries quickly, that is, the base material N1 is stuck to the second polymer adhesive N3 and the nanofiber N4 in a subsequent step. It was not enough and often peeled off.
Therefore, even if the first fibrous polymer adhesive N2 is quick-drying, it is necessary to completely complete solidification (curing) by the time it moves to the next step. Therefore, in detail in the next step. A step [first polymer adhesive cooling step C] of spraying the first fiber-like polymer adhesive N2 to be described to cool the first fiber-like adhesive is provided.
Further, the reason why the first polymer adhesive N2 forms a spider web-like or zigzag-like network in the space of the square network in the base material N1 is that the space formed by the nanofiber N4 is less likely to be blocked. Therefore, if the space of the mesh of the base material N1 itself is reduced, the weight of the shielding member is increased, and the shading rate is increased.

The net-like reinforcing fiber forming portion 2 in which the spider web-shaped or zigzag-shaped fibers are stretched around will be described with reference to FIGS. 1, 2 and 3.
As shown in FIG. 1, the reticulated reinforcing fiber forming portion 2 is located between the [base material feeding step A] and the [cooling step C of the first polymer adhesive], and is a polypropylene (or polyproethylene) group. Since the first polymer adhesive N2 is sprayed onto the mesh surface of the material N1 to form a fine mesh in the square space of the base material N1, the nanofibers N4 and the second polymer adhesive N3 are adhered to each other. Immediately before the agent is sprayed onto the base material N1, as shown in FIGS. 2 and 3, the agent is sprayed onto the base material N1 from the nozzle portion 22 in the form of fibers slightly thicker and stronger than the nanofibers.

This first fibrous polymer adhesive N2 is a polyurethane hot melt adhesive (moisture curing type) (PUR reactive hot melt (product number) No. 703.5) manufactured by Cliverit Japan Co., Ltd., and has the following physical properties. Is.
(A) Main component Polyurethane viscosity
120 ℃: 11,000 mPas
140 ℃: 6,000 mPas
Open time (required (curing) time to evaporate solvent) φ3 mm bead: 30 sec Open time 90 μm: 30 sec
Features: Heat resistance, water resistance, cold resistance, low temperature coating, elastic type, stringiness

When spraying the first fibrous polymer adhesive N2, if the gaps between the nanofibers N4 are filled, the good air permeability of the nanofibers N4 will be hindered. It is important that the agent N2 is formed as thin as possible so as not to fill the gaps in the nanofibers N4 so as to form a spider web-like or zigzag-like net.
The first fibrous polymer adhesive N2 was PUR-reactive hot melt ((product number) No. 703.5), but the selection conditions were:
(1) Reinforcement of the mesh space (between meshes) of the base material N1 and expansion of the adhesive-coated surface (expansion of the adhesive area) of the second polymer adhesive N3, which will be described later, can be measured, and (2) in the form of fibers. Strong stringiness and excellent cross-linking property, (3) Adhesion because the distance from the first polymer adhesive spraying step to the second nanofiber-like polymer adhesive N3 spraying step is short. It is necessary that the surface is cured immediately after the agent is applied. As the other first polymer adhesive N2, the same result was obtained with the polyurethane hot melt adhesive (moisture curing type) of the non-yellow discoloration type (transparent or white) part number VP9484 / 10 manufactured by Cliverit Japan Co., Ltd. was gotten.

In FIG. 1, the spraying portion 21 of the first fibrous polymer adhesive N2 of the net-like reinforcing fiber forming portion 2 is arranged above the base material N1 moving from the upper guide roller 13a to the lower guide roller 13b, and is arranged above the nozzle portion 22. Is reciprocally moved by a distance of 110 cm (nanofiber formation width) parallel to the plane of the base material N1 to which the fibers move together. This is because the first polymer adhesive N2 does not need to be laminated like the nanofiber layer, and it is sufficient that the strength of the nanofiber N4 is reinforced, and it is better that the amount is less.
The viscosity of the above-mentioned first nanofiber-like polymer adhesive N2 is lower at high temperatures, and the viscosity at 140 ° C. is 6000 (mPa · s). 22 is provided with a heater (heater) 264. The first fibrous polymer adhesive N2 needs to be quick-drying (several seconds) so as not to melt and fuse with the second fibrous polymer adhesive N3 described later.

Here, the details of the polymer resin spraying portion 21 and the nozzle portion 22 of the first fibrous polymer adhesive N2 (adhesive) will be described with reference to FIGS. 1, 2 and 3, but at about 140 ° C. The heated adhesive (first polymer adhesive N2) is supplied from the supply unit 24 to the center nozzle 221 having a tip nozzle diameter of 0.15 mm from the adhesive (first polymer adhesive N2) supply pipe 241 by the supply pump 242. NS. A tubular hot air blowing portion 26 is provided so as to wrap the outer cylinder at the tip of the central nozzle 221. High-speed heating air H is injected from the hot air blowing nozzle portion 261 of the hot air blowing portion 26 to melt the adhesive from the central nozzle 221. Is made into a nanofiber-like polymer adhesive N2 so as to be pulled out, and is sprayed toward the base material N1. 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 used at 50 liters / minute via the heated air generator 281, the heated air supply pipe 282, and the heated air introduction portion frame 272. High-speed heated air H is introduced from the hot air outlet nozzle portion 261 at the tip of the heated high-speed air outlet 263 introduced into the high-speed air outlet passage formed between the forming cap 27 and the molten resin introduction pipe 23 and connected to the high-temperature high-speed air outlet 263. It is spouted.
The ejection area of the air blowing nozzle portion 261 ^{is set to about 1 mm 2,} and the entire nozzle portion 22 is adjusted to a high temperature of about 140 ° C. by the heater 264 while the ejected air is also heated to about 140 ° C. and ejected, and the adhesive is ejected to the nozzle portion. The temperature is maintained at 140 ° C. even at the tip of 22. 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 become turbulent from the outside near the tip of the nozzle portion 22.

Further, as described above, the hot air introduction groove 232 connected to the nozzle portion 22 is provided on the outer peripheral portion 231 on the downstream side of the molten resin introduction pipe 23 having the molten resin introduction path 234 connected to the nozzle portion 22 of the adhesive at the center. At the other end of the hot air introduction groove 232, the hot air generator 281 communicates with the hot air generator 281.
As shown in FIG. 4, the hot air introduction groove 232 is obtained by flatly cutting the outer peripheral portion 231 of the molten resin introduction pipe 23 having a circular cross section, and in this embodiment, four long hot air introduction grooves 232 are formed. There is. The hot air introduction groove 232 has a good structure of facing each other, and since the hot air is blown out from the nozzle portion 22 of the high-speed hot air blowing so as to intersect with each other, it acts to stretch the molten polymer material of the adhesive. Further, since the long hot air introduction groove 232 is formed, the hot air is orderly blown out from the nozzle portion 22.
With such a configuration, it was found that the adhesive was produced in a large amount in the form of fibers having a fiber diameter of 500 nm to 500 μm, although it was slightly thicker than this method without using the ESD method, and from 10 μm among them. The first polymer adhesive N2 melted in the form of 100 μm fibers is sprayed onto the polypropylene base material N1 so as to adhere in a spider web shape or in a zigzag shape, and is uniformly applied to the entire surface.

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 surround 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 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 the discharge port 2212 protruding from the high-speed air outlet 263 is such that the high-speed hot air blowing passage 262 of the heated air passage forming cap 27 is oblique, and the central nozzle body 221 has an oblique amount X. Since the outer circumference is also oblique, a washer 273 for fine adjustment of the hot air outlet is interposed between the heating air passage forming cap 27 and the frame 272 of the heating air introduction portion, and the thickness of the washer 273 for fine adjustment is different. The protrusion amount X can be adjusted by selecting one or adjusting the number of sheets. At the same time as adjusting the protrusion amount X, the space between the inner wall of the high-speed hot air blowing passage 262 hot air blowing passage 21 and the outer circumference of the nozzle body 221, that is, the opening area of the hot air blowing nozzle portion 261 can be finely adjusted.
In this way, the amount of hot air blown out from the hot air blowing nozzle portion 261 can be finely adjusted. Therefore, as shown in FIG. 1, the amount of hot air blown out from the plurality of nozzle portions 22 can be made the same, and more uniform adhesion can be achieved. It is possible to produce a laminate of nanofibers of an agent and a molecular material.

Further, the nozzle portion 22 is mainly composed of 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 from the nozzle body 221 in the longitudinal direction. A central shaft hole 2211 is provided, and a discharge port 2212 is provided at the tip of the central shaft hole 2211 on the downstream side. Here, the material of the nozzle body 221 is important, but the material of the nozzle body 221 in the spinning nozzle portion 22 of the present invention is optimally ceramic or ruby, which is ruby in this embodiment.
The inner diameter of the nozzle of the discharge port 2212 was changed from 0.13 mm to 0.18 mm, but if it is 0.18 mm or more, it is difficult to generate nano-unit fibers, and if it is 0.13 mm or more, the polymer adhesive melted in the inner diameter of the nozzle. In this example, it was set to about 0.15 mm because it would be clogged. Further, in the above-mentioned Patent Document 4 described above, the inner diameter of the nozzle is set to 0.15 mm, but since the material is stainless steel, it is found that the quality of the fiber is immediately changed to a thick fiber. It was found that this is due to the fact that the inner diameter of the stainless steel nozzle expands due to repeated loading and pressure. Therefore, by using ruby (ceramic), which has excellent heat resistance and abrasion resistance and does not deform even at high temperatures, it was possible to produce a high-quality polymer nanofiber laminate N5 even after continuous operation for a long time.
Since the base material N1 has a coarse mesh, the first fibrous polymer adhesive N2 passes through the base material N1 and is collected behind by the adhesive collecting unit 25.

However, it is difficult to process ceramics and rubies, 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 is provided at the upstream end of the nozzle body 221 and protrudes inward at the downstream end of the inner hole 2221 of the corresponding nozzle support 222. A stop portion 2222 is provided, and the nozzle body 221 is inserted through 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. Due to such a structure, the nozzle body 221 does not separate from the nozzle support 222 even if the molten polymer is inserted at a high pressure on the downstream side. 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 adhesive supply unit 24 sends the supply pump 242 and the adhesive. It is connected and supplied by the supply pipe 241.
The number of nozzle main bodies 221 can be reduced by moving the nozzle main body 221 horizontally with respect to the base material N1 while maintaining the same distance as necessary.
Next, in order to cool the first fibrous polymer adhesive, the process proceeds to [first polymer adhesive cooling step C].

[First Polymer Adhesive Cooling Step C]
In this embodiment, the cooling device 4 in the [first polymer adhesive cooling step C] uses a Perche element.
As shown in FIG. 5, the surface temperature of the aluminum plate cooling plate 31 is cooled to −10 ° C. to −20 ° C., and the heat insulating plate 32 is arranged to face the cooling plate 31 so that the interval between them is 5 mm or less. The distance between the net-like reinforcing fiber obtained by applying the first fiber-like polymer adhesive N2 to the base material N1 in the previous step, the cooling plate, and 31 should be 1.5 mm or less, that is, the first fiber-like polymer adhesive N2. It is also preferable from the viewpoint of promoting curing of the fiber and saving energy.
A cooling mechanism 33 for a pelche element is incorporated behind the cooling plate 31, but as the principle of the pelche element is shown in FIG. 6, the pelche device 34 is composed of, for example, a plurality of pelche elements, and a plurality of Ns are used. The type thermoelectric semiconductor (n) 341 and the P-type thermoelectric semiconductor (p) 342 are arranged alternately, and they are connected in a staggered manner by metal electrodes 343 to supply DC power from the power supply 345 to both ends. There is. In this connected state, as shown by the arrow pointing to the right in FIG. 6, since the electrons and holes in the semiconductor carry heat downward, the metal electrode 343u on the left side is cooled and the metal electrode 343d on the right side is heated.
A plurality of upper surfaces of the left side metal electrode 343u are connected and covered with a thin plate-shaped insulating material 344, and are superposed so as to be in close contact with a cooling plate 31 for heating and cooling through the insulating material 344 so as to efficiently conduct heat. ing. Similarly, a plurality of upper surfaces of the right metal electrode 343d are connected and covered with a thin insulating material 344 so that heat is efficiently conducted to a cooling plate 31 that cools (endothermic) (heats) through the insulating material 344. They are stacked so that they are in close contact with each other.
This [first polymer adhesive cooling step C] is very important, and the microphotograph 11A when passing through this [first polymer adhesive cooling step C] shows the second adhesive nanofibers. While it is reinforced with a spider web-like mesh, the second adhesive is crimped in the microscopic photograph 11B when [the first polymer adhesive cooling step C] does not exist (does not operate). Since it does not have a spider web shape, it can be seen that it is not a strong reinforcement.
The net-reinforced base material N1 is promoted to solidify (harden) the adhesive, and a step of spraying a second fibrous polymer adhesive N3 for adhering the next second adhesive nanofiber [second polymer adhesive] The process proceeds to the spraying process D].

[Second polymer adhesive spraying step D]
Next, in the [reticulated reinforcing fiber forming step B], the second fibrous polymer adhesive N3 for adhering the nanofibers is sprayed onto the base material reinforced with the first fibrous polymer adhesive N2 [second polymer]. Adhesive spraying step D] will be described.
This state is as shown in FIG. 12 (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3) of the microphotograph, and is a fiber of 10 μm to 100 nm thinner than the first fibrous polymer adhesive N2. The adhesive of the second fibrous polymer adhesive N3 having a diameter is sprayed thinly on the net and contracted so as not to close the gap. In this way, the second fibrous polymer adhesive N3 adheres and shrinks while the adhesive N2 clings 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 of FIG. 13 further shows that the adhesive of the second polymer adhesive N3 has a mesh. It is sprayed thinly so as not to block the gap.
As shown in FIG. 1, the apparatus configuration of the [second polymer adhesive spraying step D] is located between the [first polymer adhesive cooling step C] and the [nanofiber generation step E], and is a nozzle. Is basically the same as in [Reinforcing Fiber Forming Step B], and the second fibrous polymer is adhered to the surface that becomes the mesh between the polypropylene (or polyproethylene) base material 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 curable type) (PUR reactive hot melt (product number) No. 701.1 or 701.2) manufactured by Cliverit Japan Co., Ltd., and has the following physical properties. It is like. In this example, UR reactive hot melt (product number) No. 701.2 was used. As another second polymer adhesive N3, the same result was obtained with a polyurethane hot melt adhesive (moisture curing type) of Henkel Co., Ltd.'s non-yellow discoloration type (transparent or white) product number LA7575UV. ..
(B) PUR Reactive Hot Melt (Product No.) No.701.1 Principal 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 (at the time of manufacture)
brookfield HBTD 10rpm 100 ℃ Approx. 5,000 ± 1,500mPas 120 ℃ Approx. 3,000 ± 1,000mPas Open time. Φ3mm Bead: 3-4sec Additive: Contains isocyanate.

The second polymer adhesive N3 was PUR-reactive hot melt (product number: No. 701.1 or 701.2), but the selection conditions were:
(1) Good adhesion between the mesh space (between meshes) of the base material N1 and the base material of the reinforcing mesh made by cross-linking the first polymer adhesive N2, and (2) without blocking the mesh. There is little deformation such as stringiness, (3) It takes a long time for the surface to harden after applying the second polymer adhesive N3, and it takes a relatively long time (3 minutes to 1) for the surface to harden. (Time) is used to apply nanofibers to maintain a long time for the base material N1 and nanofibers N4 to adhere and cure. It is necessary that the nanofiber N4 sprayed with titanium oxide is easily adhered.
Therefore, other polymer adhesives may be used as long as they satisfy these conditions and can form fibers having a fiber diameter of 500 nm to 10 μm.

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

As described above, in the formation of the adhesive of the second fibrous polymer adhesive N3, it is important to make the adhesive thin enough so as not to block the space formed by the nanofiber N4 as much as possible, and the film spreads out. If the adhesive that forms the shape is used, there is no point in using the nanofiber N4, and it is preferable that the fiber is as thin as possible. In this embodiment, it is important that the second polymer adhesive N3 is a fiber having a fiber diameter of 500 nm to 10 μm and is sprayed thinly on the reinforced base material so as not to close the gap to facilitate shrinkage.
In short, it is an absolute requirement that the first fibrous polymer adhesive N2 and the second fibrous polymer adhesive N3 form fine fibers, but in particular, the first fibrous polymer adhesive N2 has a mesh. Therefore, it is desirable that the second fiber-like polymer adhesive N3 has an adhesive function and maintains a fiber-like shape and is immediately cured. On the contrary, the second fiber-like polymer adhesive N3 is a base material N1 or a first fiber. It is desirable to enhance the function of adhering the state polymer adhesive N2 and the nanofiber N4, maintain a sufficient adhesion time, and cure relatively slowly. As shown in FIG. 1, this embodiment also has a configuration in which a sufficiently long distance is transferred before winding.
That is, in this embodiment, the distance from the adhesive supply unit 24 to the nanofiber laminate winding unit 7 is 10 to 20 m, and the moving speed of the base material N1 is 80 cm / min to 150 cm / min. The distance from the adhesive supply unit 24 to the nanofiber laminate winding unit 7 is 15 m, the moving speed of the base material 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 of the nozzle itself of the first polymer adhesive N2 and the setting conditions are as shown in FIG. However, the structure itself is the same as that of the nozzle portion 22 and the air blowing nozzle portion 261 of FIGS. 2 and 3, except for the second polymer resin spraying portion 21b, and thus the description thereof will be omitted.

[Nanofiber generation step E]
The nanofiber generation step E mainly includes a nanofiber generation step E1 and a nanofiber collection step E2.
[Nanofiber generation step E1]
The [second polymer adhesive spraying step D] is completed, and the state as shown in FIG. 12 (base material N1 + (crosslinking adhesive) N2 + (adhesive) N3) of the microphotograph is displayed. The polyvinylidene fluoride (PVDF) nanofibers produced in the above are sprayed and laminated.
This state is a micrograph as shown in FIGS. 13 and 14 (base material N1 + (crosslinked adhesive) N2 + (adhesive) N3 + nanofiber N5 sprayed with titanium oxide).
The device configuration of [Nanofiber generation step E1] of [Nanofiber generation unit E] will be described. In this nanofiber generation step E1, the configuration of the nozzle portion is roughly the same as that of the network-like reinforcing fiber forming step B, and the main components are The difference is that in order to stretch the raw material polymer, instead of melting at temperature like an adhesive, a polymer that is dissolved in a solvent to dilute its viscosity is spun, and a polymer having this long molecular arrangement is spun. Since the material is dissolved in a solvent and pressurized to be 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 the high-speed air for stretching is also hot. No need to heat to. Here, first, the spinning nozzle portion 4 will be described.

[Nanofiber spinning nozzle part]
In the nanofiber spinning nozzle part, the polymer material is not melted but melted, and the operating temperature is 30 ° C to 38 ° C, so it is different from heating the polymer material of the adhesive to about 300 ° C to melt it. 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. A feeding port 43 is provided on the opposite side of the shaft hole 4211, and polyvinylidene fluoride (PVDF) dissolved in a solvent is supplied to the feeding port 43. As shown in FIG. 7, the feed route of the dissolved polyvinylidene fluoride (PVDF) to the feed port 43 was such that the polyvinylidene fluoride (PVDF) was warmed to 20 ° C. at room temperature or slightly warmed by the dissolved polymer supply unit 44. It is heated to about 40 ° C., then fed from the dissolved polymer supply unit 44 via the dissolved polymer supply pipe 441 by a gear pump 442 or the like, and further melted via the dissolved polymer supply unit 44 after feeding. The prepared polyvinylidene fluoride (PVDF) is supplied to the above-mentioned dissolved polymer introduction tube 43.
The dissolved polymer introduction pipe 43 is provided with a hot water heat insulating portion 45 to maintain the nozzle portion 42 at 30 ° C. to 38 ° C., and the nozzle portion 42 is distributed by a water heater 452 equipped with a heater pump 451. It is provided in the vessel 453 to maintain the temperature. As shown in FIG. 7, this arrangement is circulated so as to be connected in series from the hot water outlet 454 by a pipe 455 and returned to the hot water return port 456.

Here, the reason why hot water is used to maintain the temperature of the dissolved polymer introduction pipe 43 is that the temperature control is relatively easy and unlike the heater and the like, the environment is not dried.
Further, the six nozzle portions 42 in one row in the vertical direction and the hot water headquarters 45 and the like connected thereto are integrated, and the flat surface holding grid (or the flat surface holding grid (or) is provided by the lower left and right traverse mechanism (nozzle portion 42, hot water heat retaining portion 45) 457. The thickness of the nanofiber laminate is made uniform by constantly moving in the range of 7.5 cm to 15 cm in parallel with the wire mesh) 51. Further, the distance from the nozzle portion 42 to the plane holding grid (or wire mesh) 51 of the nanofiber collecting device 5 is set to about 165 cm, the polymer material described later is sufficiently stretched, and the solvent toluene or the like is used as the polymer material. I try to scatter from.
In order to reduce the viscosity of polyvinylidene fluoride (PVDF) in Example 1, NMP is used as a solvent and the material concentration is 14 wt%, as will be described later. Further, the inner diameter of the discharge port 4212 is set to 0.1 mm to 0.2 mm, and in this embodiment, it is 0.15 mm. However, if it is 0.2 mm or more, it is difficult to obtain nano-order fineness even if it is stretched, and the thinner one is. It is good, but if it is 0.1 mm or less, it will clog and the spinning speed will slow down.

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

Further, the nozzle portion 42 of the stretching airflow means is mainly composed of the nozzle body 421 and the nozzle support 422, and as shown in the enlarged view in the vicinity of the discharge port 4212 in FIG. 8, the nozzle body 421 has a melting height in the longitudinal direction. A central shaft hole 4211 from which molecules are ejected is provided, and a discharge port 4212 is provided at the tip on the downstream side of the central shaft hole 4211. The optimum material for the nozzle body 421 in the nozzle portion 42 of the present invention is ceramic or ruby, which is ruby in this embodiment.
The inner diameter of the nozzle of the discharge port 4212 was changed from 0.13 mm to 0.18 mm, but if it was 0.18 mm or more, it was difficult to form a fibrous adhesive in nano units, and if it was 0.13 mm or more, it melted into the inner diameter of the nozzle. Since the polymer is clogged, it was set to about 0.15 mm in this example. Further, in the above-mentioned Patent Document 4 described above, the inner diameter of the nozzle is set to 0.15 mm, but since the material is stainless steel, it is found that the quality of the fiber is immediately changed to a thick fiber. It was found that this is due to the fact that the inner diameter of the stainless steel nozzle expands due to repeated loading and pressure. Therefore, by using ruby (ceramic), which has excellent heat resistance and abrasion resistance and does not deform even at high temperatures, it was possible to produce a high-quality polymer nanofiber laminate N5 even after continuous operation for a long time.

However, it is difficult to process ceramics and rubies, 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 collar portion 4213 is provided at the upstream end of the nozzle body 421 and protrudes inward at the downstream end of the inner hole 4221 of the corresponding nozzle support 422. A stop portion 4222 is provided, and the nozzle body 421 is inserted through 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. Due to such a structure, the nozzle body 421 does not separate from the nozzle support 422 even if the molten polymer is inserted at a high pressure on the downstream side. 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.
Further, the resin dissolved by an appropriate means is supplied to the dissolved polymer introduction pipe 43 communicating with the nozzle portion 42.
The number of nozzle bodies 421 can be increased by moving the nozzle body 421 in the horizontal direction at the same distance with respect to N3 in which the second fibrous polymer adhesive is sprayed on the base N1 as needed. Can be reduced.
A spacer portion (not shown) for maintaining a passage gap is provided at an appropriate position 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 wind blowing passage 462. Is maintained to form a high-speed wind blowing passage 462.

To further explain this stretched airflow means, since the polyvinylidene fluoride (PVDF) fiber is further stretched by the high-speed airflow, the blowing angle of the ring-shaped high-speed wind outlet 463 (the total angle of the left and right sides about the axis of the central shaft hole 4211). However, as a result of the experiment, the angle is about 30 ° to 60 °, that is, the blowing direction of the high-speed airflow at the high-speed wind outlet 463 is 15 ° to 30 ° with respect to the central axis of the discharge port 4212 of the central axis. When the angle is 30 ° (15 ° with the central axis) or less, the contact force with polyvinylidene fluoride (PVDF) is small and the stretching action is small, and the angle is 60 ° (30 ° with the central axis) or more. In that case, since no negative pressure is generated in contact with the material, the stretching action is still small, and in the first embodiment, the stretching action works efficiently by setting the angle at 38 ° (angle 19 ° with the central axis).
As described above, if the airflow from the high-speed wind outlet 463 does not hit the appropriately spun polyvinylidene fluoride (PVDF) fiber, it ends up with microfibers on the order of μ and does not become nanofibers.
Further, in order to efficiently stretch the 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 the polyvinylidene fluoride (PVDF) fiber in a dissolved state, and the diameter of the gear pump 442 is increased. It must be possible to discharge the dissolved polyvinylidene fluoride (PVDF) from the 0.15 mm discharge port 4212.

Further, the stretched airflow means needs to be stretched from the discharge port 4212 with the high-speed jet air J even after spinning, but more importantly, the solvent such as NMP contained in the polyvinylidene fluoride (PVDF) fiber is vaporized while stretching. Therefore, the high-speed wind outlet 463 needs to be slightly projected from the discharge port 4212 of the spinning nozzle portion 42 by about X1 = 4 mm (2 to 4 mm), and the polyvinylidene fluoride spun from the discharge port 4212. It is configured to promote the vaporization of the solvent of the vinylidene (PVDF) fiber or the drying of the polyvinylidene fluoride (PVDF) fiber.
If the predetermined distance X1 in the flow direction between the high-speed wind outlet 461 and the discharge port 4212 is 5 mm or more, the stretching action of the PVDF fiber due to the high-speed wind is weakened, and if it is 1 mm or less, the promotion of solvent vaporization is weakened. The fibers themselves curl and adhere, making it difficult to form beautiful PVDF nanofibers. As described above, it is important to achieve both the stretching of polyvinylidene fluoride (PVDF) fibers and the rapid removal of the solvent.
As shown in FIG. 7, it is formed in the 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 and a length of about 7 cm in the downstream direction of the injection air passage forming cap 47. The nozzle wind tunnel 49 (hood) is attached to the male screw portion 471 of the injection air passage forming cap 47 with the mounting 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 linearly stretched, the stretching time of the resin is extended, and the fiber diameter is extremely fine. It is effective in making the fibers, and it is possible to prevent interference with high-speed wind discharged from other nearest nozzles, and as a result, a uniform nanofiber laminate can be obtained. Then, when a solvent such as NMP is vaporized and removed from the polyvinylidene fluoride (PVDF) fiber, the drawing is completed and the nanofiber collecting portion of the [nanofiber collecting step E2] of the downstream nanofiber laminate forming step E is completed. Collected at 5.

[Nanofiber collection process E2]
As shown in FIG. 1, the nanofibers blown from the nozzle portion 42 and the high-speed air blowing nozzle portion 461 are collected by the downstream nanofiber collecting device 5.
The nanofiber collecting device 5 is provided with a flat surface holding grid (or wire mesh) 51 having fine through holes facing the nanofiber N4 to be sprayed, and a suction duct 52 is provided on the back side where the nanofiber N4 is sprayed. Has been done.
Feed rollers 13c are provided upstream and feed rollers 13d are provided downstream at both ends of the above-mentioned flat surface holding grid (or wire mesh) 51, and the drawn base material N1 such as a non-woven fabric is provided on the flat surface holding grid (or wire mesh). The product nanofiber N5, which is placed on 51 and the laminated body of nanofiber N4 is placed on the upper surfaces of the base materials N1, N2, and N3 and moved, and then sprayed with the deodorant in the next [Deodorant attachment step F]. It is sent to the winding [nanofiber winding step G].

[Deodorant attachment process F]
Titanium oxide is attached to the nanofiber laminate before the second fibrous polymer adhesive N3 of the produced nanofiber laminate is completely cured in the nanofiber collection step E2. Conventionally, zinc oxide was kneaded into polyvinylidene fluoride (PVDF), but since it adheres near the surface of the fiber, it also has a deodorizing effect. In addition, when titanium oxide near the surface of nanofibers is irradiated with light, active oxygen such as OH radicals is generated, and these OH radicals have much stronger oxidizing power than chlorine, hypochlorous acid, hydrogen peroxide, ozone, etc. It can be understood that chemical substances that are difficult to decompose due to its oxidizing power can be safely decomposed, a deodorizing effect can be expected compared to conventional zinc oxide, and it is adhered and fixed to the surface of titanium oxide, so it is further eliminated. The odor effect is enhanced.
The deodorant attachment portion 6 will be described with reference to FIG. 9. Compressed air 65 is sent to a pressurized tank 63 in which a deodorant liquid in which titanium oxide is dissolved with toluene or the like is stored, and the compressed air 65 is sprayed from the pressurized tank 63. The titanium oxide solution is sprayed from the deodorant spray 61 onto the nanofiber laminate N4 via the agent supply pipe 64.
Specifically, this deodorant has the following composition ratio.
Deodorant (offensive odor absorber): Titanium oxide 6.6 wt /% (% of total weight: w / w%) N-methylpyrrolidone (NMP): 75.4 wt /% Toluene : 4.7 wt /%
In this deodorant spray 61, the titanium oxide solution is evenly sprayed on the surface of the nanofiber laminate N4 by the spray driving device 62, and the deodorant spray 61 is transferred to the nanofiber winding step of the next step.

[Nanofiber laminate winding process G]
The product nanofiber laminate N5 on which titanium oxide is sprayed runs 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. In this way, the take-up rod 71 of the nanofiber laminate N4 is taken up by the drive of the feed roller 72. (Fig. 1)

[Nanofiber laminate product N5]
The nanofiber laminate in the state shown in FIG. 14 (base material N1 + (crosslinked adhesive) N2 + (adhesive) N3) of the micrograph was produced under the following conditions.
Setting conditions (Example)
material:
(1) Main agent: Polyvinylidene fluoride (PVDF) manufactured by Kureha Corporation 13.3 wt /% (% of total weight: w / w%) Solvent (solvent): Made by Nippon Refine Co., Ltd. Solution discharge pressure: 0.15 MPa
High-speed airflow blowing angle 38 °
High-speed airflow pressure: 0.26 MPa
High-speed airflow flow rate: 34 L / 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, although the weather resistance was slightly inferior. As a combination of other polymers and a solvent, nylon (manufactured by Ube Kosan: 1022B) and formic acid as a solvent (solvent), similarly, polyetherimide (PEI) and DMF or dimethylacetamide (DMAc) as a solvent are also used. (PolyAcryloNitrile, PAN), Poly Ether Sulphone (PES) and dimethylacetamide (DMAc) or DMF (dimethylformamide), chitosan and weak acids such as acetic acid or citric acid. , Acrylic (PolyMethyl MethAcrylate, PMMA) and methanol, polylactic acid and chloroform combinations, etc. are possible for the production of nanofibers.

[Characteristics of thin film deodorant shielding member for building materials using nanofiber laminate N4 of this example]
The configuration of the filter using the nanofibers of this example is as follows.
(1) Base material N1: Polypropylene (PP): 0.25 mm diameter monofilament 18 mesh, thickness: 0.48 mm, weight: 80 g / m ²
(2) First Polymer Adhesive N2: Polyurethane Hot Melt Adhesive (Quick-drying Moisture Curing Type)
Fiber with 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) Fiber with a diameter of 200 nm to 50 nm: 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 base material N1 is a monofilament having a diameter of 0.25 mm, but if it is too thin, the strength is insufficient, and if it is too thick, the thickness of the product becomes large and the shading rate becomes high, resulting in darkness. The diameter of the filament is preferably 0.1 to 0.5 mm, and the coarse mesh of the woven or knitted fabric made of this mono or multifilament is preferably a mesh of 15 to 30 mesh.
The first polymer adhesive N2 is polyurethane, but an olefin adhesive may also be used, and the fiber diameter is 10 nm to 100 μm, but the weight is preferably 1 to 5 g / mm ³ , and the first polymer adhesive. In order to form a mesh, N2 should have a relatively fast curing / drying speed of about several seconds (sec), which is relatively fast.
The second polymer adhesive N3 and polyurethane are used, but an olefin adhesive may also be used, and the fiber diameter is 500 nm to 10 μm, but the weight is preferably 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 better that the curing / drying speed is about 1 hour (sec) or more, which is relatively slow.
Further, titanium oxide was dissolved in toluene in nanofiber N4 and sprayed 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 acid is dissolved. It is preferable that the nanofiber laminate N4 can be easily sprayed and fixed by spraying toluene and has excellent weather resistance. The fiber diameter was 200 nm to 1 μm and the weight was 0.8 g / mm ³ , but it is preferable that the nanofiber laminate has a low light-shielding property and a high collection rate of pollen and the like.

Since it has the above configuration, it is sufficiently thin as a whole because it is adhered to the base material N1 even though it is a very thin shielding member of about 1 μm as compared with the thickness of the base material N1 of 0.3 mm. Has strength.
The actual thickness of the final product (base material N1 + first polymer adhesive N2 + second polymer adhesive N3 + nanofiber N5 sprayed 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 has increased to only 0.12 mm, it is extremely thin, and the shading rate can be extremely low.
In addition, the UV shading rate is 58% (spectrophotometer / all wavelength range averaging method by unified evaluation method of processing effect of UV cut material (Japan Chemical Fibers Association), band pass filter installed between integrating sphere and detector). Yes, the transmittance is 38.9% at the wavelength of 305 nm, and the transmittance is 44.1% at the wavelength of 360 nm. The shading rate is 64.62% (illuminance after mounting 3538lx) (JIS L1055A method: illuminance before mounting the test piece: 10000lx. Light source side of the test piece: coated surface), and this value is the thinnest light transmission of commercially available curtains. From the fact that the rate is 55 to 70%, it can be seen that the light from the outdoors is sufficiently taken in.

The air permeability is 423.8 ^{cm 3} / cm ² · s, which is sufficient compared to the filter effect, but the pollen collection (filtration) efficiency of the present invention is 89.1%, which is also from the test results. It is clear and can be used as a material for building materials that prevent the invasion of pollen and fine insects.
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 unit at a constant speed. The mass of the particles captured by the filter unit and the mass of the particles passed through the filter unit were measured, and the collection (filtration) efficiency was calculated using the following formula.
Pollen particle capture (filtration) efficiency% = Particle mass captured in the filter section (mg) / (Particle mass captured in the filter section (mg) + Particle mass passed through the filter section (mg)) Test conditions Test powder Body (pollen substitute particles): Matsuko Ishi (APPIE standard powder) Test fluid: 28.3 L / min
Large amount of test powder: 75 ± 5 mg
Test powder rate: 20 ± 5 mg / min
Laboratory temperature and humidity: 20 ± 5 ° C, 50 ± 10% RH

The deodorant property, which is a feature of the present embodiment (the present invention), will be described.
First, the ammonia gas removal performance evaluation test was carried out by requesting the Kaken Test Center, a general incorporated foundation, to apply the method specified in the SEK mark textile product certification standard ((one company) Textile Evaluation Technology Council) mutatis mutandis. However, the sample amount is "90 sheets of 10 cm x 10 cm + 10 sheets of 10 cm x 3 cm", the type of bag used is Smart Bag PA (manufactured by GL Sciences), and the test conditions of the ammonia gas removal performance evaluation test are the same ammonia. In an atmosphere of a predetermined volume (200 ml) with an initial concentration of 100 ppm of gas, the state in which the sample amount of this example is present and the state in which nothing is present as a conventional example and a comparative example (blank test) are left for 2 hours. The following table compares the gas concentrations.
Ammonia gas removal performance evaluation test Test target sample Initial concentration (ppm) Gas concentration after 2 hours (ppm) Decrease rate (%)
Example 100 1.0 ≧ 99
Conventional example (kneaded with zinc oxide)
100 15 81
Comparative example (blank) 100 80 ---
As described above, the concentration of ammonia gas is reduced by 99% with respect to the empty state, which is a remarkable effect compared to the 81% reduction of the conventional nanofiber laminate kneaded with zinc oxide. It turns out that there is.

Next, a hydrogen sulfide gas removal performance evaluation test was conducted, but the method specified in the SEK mark textile product certification standard ((one company) Textile Evaluation Technology Council) was applied mutatis mutandis, and the Kaken Test Center was requested. carried out. However, the sample amount is "90 sheets of 10 cm x 10 cm + 10 sheets of 10 cm x 3 cm", the type of bag used is Smart Bag PA (manufactured by GL Sciences), and the test conditions of the hydrogen sulfide gas removal performance evaluation test are the same. In an atmosphere of a predetermined volume (200 ml) having an initial concentration of hydrogen sulfide gas of 4.0 ppm, the state in which the sample amount of this example was present and the state of 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 target sample Initial concentration (ppm) Gas concentration after 2 hours (ppm) Decrease 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% with respect to the empty state, which has a remarkable effect.

As described above, the thin film deodorant shielding member of the embodiment of the present invention has a sufficient deodorizing effect, has sufficient air permeability, lowers the shading rate, and increases the collection efficiency of pollen particles. can. In addition, since the nanofiber material is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is 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. , Easy to clean.
Here, polyvinylidene fluoride (PVDF) is one of the thermoplastics and has a melting point, in which titanium oxide is dissolved in toluene and sprayed on polyvinylidene fluoride (PVDF) as a material for the nanofiber laminate N4 and fixed. This is a high-strength resin with a temperature range of 134 to 169 ° C. The heat-resistant temperature that can be used regularly is around 150 ° C, and it is a material with good thermal stability. It is also familiar, has good chemical resistance, has excellent workability, is flame-retardant, and emits less smoke even when burned. It has good electrical characteristics, excellent ferroelectricity and piezoelectricity, and in particular, it has excellent weather resistance and is 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. The screen is easy to clean.

As described above, the thin film deodorant shielding member of the embodiment of the present invention has a sufficient deodorizing effect, has sufficient air permeability, lowers the shading rate, and increases the collection efficiency of pollen particles. can. In addition, since the nanofiber material is polyvinylidene fluoride (PVDF), it has excellent weather resistance and is 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. , Easy to clean.
Needless to say, the present invention is not limited to the above examples as long as it does not impair the characteristics of the present invention.

A ... Base material feeding process, B ... Reticulated reinforcing fiber forming process, C ... First polymer adhesive cooling process, D ... Second polymer adhesive spraying process, E ... Nanofiber generation process, F・ ・ Deodorant attachment process, G ・ ・ Nanofiber laminate winding process, H ・ ・ High-speed heating air, J ・ ・ High-speed injection air,
N1 ... Base material, N2 ... First fiber-like polymer adhesive (base material), N3 ... Second fiber-like polymer adhesive (base material), N4 ... Nanofiber laminate, N5 ... Product Nanofiber laminate,
1 ... Base material supply part, 11 ... Winding rod, 12 ... Feed roller,
13 (a, b, c, d) ... Guide roller, 14 ... Tension adjustment mechanism,
2. Reinforcing fiber forming part,
21 ... 1st polymer resin spraying part,
(21b ... 2nd polymer resin spraying part) 22 ... Nozzle part,
221 ... Nozzle body, 2211 ... Central shaft hole,
2212 ... Discharge port, 2213 ... Collar, 222 ... Nozzle support,
2221 ... Inner hole, 2222 ... Locking part, 2223 ... Opening,
2224 ... Outer circumference,
23 ... molten resin introduction pipe, 231 ... outer circumference, 232 ... hot air introduction groove, 234 ... molten resin introduction path, 24 ... adhesive supply part, 241 ... adhesive supply pipe,
242 ... Supply pump 25 ... Adhesive collector,
26 ... hot air blowing part, 261 ... hot air blowing nozzle part,
262 ... High-speed hot air outlet, 263 ... High-speed air outlet,
264 ... Heater,
27 ... Heating air passage forming cap, 271 ... Male screw part, 272 ... Heating 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 ... Insulation plate, 33 ... Cooling mechanism,
34 ... Perche device, 341 ... N-type thermoelectric semiconductor,
342 ... P-type thermoelectric semiconductor, 343,343u, 343d ... Metal electrode,
344 ... Insulation material, 345 ... DC power supply 4 ... Nanofiber spinning nozzle part 41 ... Nanofiber spraying part,
42 ... Nozzle part, 421 ... Nozzle body, 4211 ... Central shaft hole,
4212 ... Discharge port, 4213 ... Collar, 422 ... Nozzle support,
4221 ... Inner hole, 4222 ... Locking part, 4223 ... Opening,
4224 ... Outer circumference,
43 ... Dissolved polymer introduction pipe, 431 ... Outer circumference, 432 ... Injection air introduction groove,
44 ... Dissolved polymer supply unit, 441 ... Dissolved polymer supply pipe,
442 ... Gear pump,
45 ... Hot water heat insulator, 451 ... Heater pump, 452 ... Water heater,
453 ... Distributor, 454 ... Hot water outlet, 455 ... Piping,
456 ... Hot water return port,
457 ... Left and right traverse mechanism (nozzle part 42, hot water heat retaining part 45),
46 ... High-speed wind blowing part, 461 ... High-speed wind blowing nozzle part,
462 ... High-speed wind outlet, 463 ... High-speed wind outlet,
47 ... High-speed air passage forming cap, 471 ... Male screw part,
472 ... Air introduction frame,
48 ... Air supply unit, 481 ... Air pump, 49 ... Nozzle wind tunnel,
5 ... Nanofiber collector, 51 ... Plane holding grid (or wire mesh),
52 ... Suction duct,
6 ... Deodorant attachment, 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 (5)

A mono or multifilament woven or knitted fabric selected from PP (polypropylene), polyethylene (PE), polyester (PET), and polyphenylene sulfide (PPS) is used to feed out a coarse-grained, strong substrate and cure it with moisture. spraying to the substrate in Fiber-like type of first polymeric adhesive of polyurethane hot melt adhesive by the first adhesive spray, a cooling plate in the cooling device is arranged immediately after downstream from -10 ° C. - At 20 ° C., the first polymer adhesive is cured by passing through the gap to form a finer mesh in the mesh of the base material to form a reinforcing base material.
A fiber having a diameter of 500 nm to 10 μm is applied to the base material and the reinforcing base material by spraying a second polymer adhesive, which is a moisture-curable polyurethane hot-melt adhesive having a curing time slower than that of the first polymer adhesive. As a form, the second polymer adhesive is shrunk by spraying thinly on the net formed of the first polymer adhesive so as not to close the gap.
Immediately after that, polyvinylidene fluoride (PVDF), nylon, polyetherimide (PEI), polyacrylonitrile, and polyether monkey, which are polymer materials having a long molecular arrangement on the second polymer adhesive sprayed thinly in the form of fibers. Nanofibers selected from phon and acrylic are sprayed and laminated by nanofiber spray so that the second polymer adhesive has air permeability and light transmission so as not to block the gaps between the nanofibers. The nanofibers are characterized in that the base material, the reinforcing base material, and the nanofibers are adhered to each other, and then a deodorant is sprayed on the surface of the nanofibers while the nanofibers are in a highly adhesive state before being cured. Method for manufacturing a laminate. The method for producing a nanofiber laminate according to claim 1, wherein titanium oxide is sprayed on the nanofiber laminate as the deodorant. Polyvinylidene fluoride (PVDF) is used as the polymer material, and the titanium oxide to be sprayed is characterized in that 2 to 20% by weight of titanium oxide is sprayed and adhered as a deodorant to polyvinylidene fluoride. The method for producing a nanofiber laminate according to claim 2. The mono or multifilament is polypropylene (PP) having a diameter of 0.1 to 0.5 mm, and the coarse mesh of the woven or knitted fabric by the mono or multifilament is 15 to 30 mesh. A method for producing a nanofiber laminate selected from the description. The cooling device manufacturing method of the nanofiber laminate according to claim 1, wherein the configuration of Reruko by a thermocouple.

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