JP2006257619A - Dry nonwoven fabric composed of polyphenylene sulfide nano-fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dry nonwoven fabric composed of PPS (polyphenylene sulfide) nano-fibers contributing to an improvement in capturing efficiency and prevention of clogging which are problems of conventional PPS bag filters. <P>SOLUTION: The dry nonwoven fabric is composed of the PPS nano-fibers having 1-1,500 nm average diameter of single fibers in 0-5% ratio of the single fibers having 1,500-5,000 nm diameter. The dry nonwoven fabric contains parts in which the PPS nano-fibers form a bundle structure and parts in which the nano-fibers form a dispersion structure are mixed in the dry nonwoven fabric. The parts in which the PPS nano-fibers form the dispersion structure are 5-95% of the dry nonwoven fabric surface in the dry nonwoven fabric surface. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dry nonwoven fabric in which a portion where a polyphenylene sulfide nanofiber forms a bundle structure and a portion where a dispersion structure is formed are mixed.

  Polyphenylene sulfide (hereinafter abbreviated as PPS) was initially put into practical use in engineering plastics and heat-resistant films because of its excellent heat resistance and chemical resistance, but recently, its use is expanding in the fields of fibers and paper. For example, bag filters and the like have been put to practical use for textiles, and batteries and motor insulation materials have been put to practical use for paper, and the demand is expected to expand further. In particular, a bug filter using PPS has been developed in which it is possible to suppress clogging in order to improve trapping efficiency and extend the filter life in order to trap finer soot and dust.

  For example, Japanese Patent Application Laid-Open No. 2000-79308 proposes a filter cloth for a bag filter aimed at suppressing clogging by forming a dense layer having an apparent porosity of 70% or less on the surface of the filter layer. Here, a technique is disclosed in which the fiber is shrunk by high-temperature heat treatment of the filter cloth or densified by crushing the fiber by hot pressing. Although a certain degree of effect was obtained by this, it was not yet a sufficient level.

  On the other hand, PPS is a very brittle polymer compared to polyesters and polyamides, which are general-purpose polymers, and it has been difficult to obtain fine fibers by beating compared to cellulose and aramid fibers. For this reason, Japanese Patent Application Laid-Open No. 2-99658 has also studied sea-island composite spinning using PPS as an island, but the PPS ultrafine yarn obtained here is at most 0.07 denier (corresponding to a single fiber diameter of 2.5 μm). In addition, it was difficult to obtain thin fibers compared to polyester and polypropylene. However, very recently, it has been shown that PPS nanofibers having a single fiber diameter of 100 nm or less can be obtained using polymer alloy fibers (Patent Document 1). However, the PPS nanofibers obtained here were shortened, and the fiber openability was poor even through the card as it was, and as it was, it was difficult to make a nonwoven fabric by needle punching or the like. Furthermore, it may be impossible to pass the card process itself by dropping or pulverizing the nanofiber itself in the card process.

Therefore, it has been desired to obtain a dry nonwoven fabric composed of PPS nanofibers by creating a new technology.
JP 2004-162244 A (pages 23-24)

  It is an object of the present invention to provide a dry nonwoven fabric made of PPS nanofibers that can contribute to improving the trapping efficiency of fine dust, which is a problem of conventional PPS bug filters, and preventing clogging.

The above object is achieved by the following means.
(1) A dry nonwoven fabric comprising polyphenylene sulfide nanofibers having an average diameter of 1 to 1500 nm and a ratio of single fibers having a diameter of 1500 to 5000 nm of 0 to 5%, wherein the polyphenylene sulfide is contained in the dry nonwoven fabric. -The part where the nanofibers form a bundle structure and the part where the dispersion structure is formed are mixed, and the part where the polyphenylene sulfide nanofibers form the dispersion structure on the dry nonwoven fabric surface is the surface of the dry nonwoven fabric surface. A dry nonwoven fabric that is 5 to 95%.
(2) The dry nonwoven fabric according to claim 1, wherein the average diameter of the single fibers of the polyphenylene sulfide nanofiber is 1 to 200 nm and the ratio of the single fibers having a diameter of 200 to 5000 nm is 0 to 5%.
(3) The dry nonwoven fabric according to claim 1 or 2, wherein fibers other than polyphenylene sulfide nanofibers are mixed.
(4) The dry nonwoven fabric according to any one of claims 1 to 3, wherein the fibers other than polyphenylene sulfide nanofibers are wholly aromatic fibers, liquid crystal polyester fibers, or cellulose fibers.
(5) A dry nonwoven fabric in which another fabric or sheet is laminated on the dry nonwoven fabric according to any one of claims 1 to 4.
(6) The dry nonwoven fabric according to any one of claims 1 to 4, wherein other fibers are mixed with the polyphenylene sulfide nanofiber.

  The dry nonwoven fabric composed of the PPS nanofibers of the present invention can achieve improvement in capture efficiency and suppression of clogging, which are problems of conventional PPS bag filters. Further, the dry nonwoven fabric composed of the PPS nanofibers of the present invention is applicable not only to bag filters but also to various insulating applications by taking advantage of excellent heat resistance, chemical resistance and liquid retention.

  The dry nonwoven fabric referred to in the present invention refers to a product made into a nonwoven fabric by a method other than a wet nonwoven fabric method such as a so-called papermaking method. Examples thereof include a nonwoven fabric in which short fibers are entangled with a needle punch or a water jet punch, and a nonwoven fabric obtained by laminating spun fibers as in spunbond or melt blow. Of course, a spunbond or melt blown nonwoven fabric may be used as a base fabric, and short fibers may be laminated thereon by needle punching or water jet punching, or vice versa.

  The PPS referred to in the present invention refers to a polymer having a repeating unit of a unit in which a sulfur atom (hereinafter abbreviated as S) is bonded to a phenyl group as described in JP-A-2004-231908, and is partially crosslinked. May be. Further, this repeating unit is preferably 70 mol% or more in the polymer, but other units can be contained in the range of 30 mol% or less as exemplified in Chemical Formula 2 of JP-A-2004-231908. is there. In addition, the PPS used in the present invention is preferably a linear type having few molecular chain branch structures from the viewpoint of ensuring spinnability during production. Furthermore, it is preferable that the molecular chain terminal of PPS is blocked with a metal ion or the like because the spinnability is improved. The molecular weight of PPS is not particularly limited as long as it can be spun, but a weight average molecular weight of 10,000 to 100,000 is preferable because both spinnability and yarn strength can be achieved. The PPS used in the present invention can be obtained using a known method as described in JP-A No. 2004-231908.

Moreover, the nanofiber said by this invention means the fiber whose fiber diameter of a single fiber is 5000 nm or less. And in this invention, it is important that the average diameter of a single fiber is 1-1500 nm. Here, the average diameter of the single fiber can be determined as follows. First, the diameter in terms of a circle is obtained from the cross-sectional area of each single fiber by, for example, image analysis of a cross-sectional photograph of the fiber. And the diameter of 300 single fibers extracted at random is averaged on the basis of the area of a cross section, and an average diameter can be calculated from this. Here, when the average diameter is calculated by the number average, the contribution of thin fibers is excessively reflected, but in order to increase the contribution of thick fibers, the average diameter is determined by area average in the present invention. More specifically, when the cross-sectional area of each single fiber is S _i , the average cross-sectional area (S _av ) of the single fiber is obtained from ΣS _i (i = 1 to n) / n, and the average diameter (D _av ) is obtained by D _av = (4S _av / π) ^1/2 . It is preferable that n is 300 or more because accuracy is improved. In addition, when it is difficult to obtain a cross-sectional photograph of a fiber, a side photograph of the fiber can be used.

  And by making the average diameter of a single fiber 1500 nm or less, when processing into a bag filter or a liquid filter, it becomes possible to capture fine particles efficiently. From the viewpoint of capturing fine particles, the thinner the nanofibers, the smaller the distance between single nanofibers, which is preferable. The average diameter of the single fibers is preferably 900 nm or less, more preferably 500 nm or less, still more preferably 200 nm or less, most preferably Preferably it is 100 nm or less. In the present invention, it is important for the PPS nanofibers to have a mixture of the part where the bundle structure is formed and the part where the dispersion part is dispersed. However, the thinner the nanofiber, the easier it is to form the bundle structure. When the average diameter of the single fibers is 200 nm or less, the force of aggregation of the PPS nanofiber single fibers becomes strong. When the average diameter is 100 nm or less, a bundle structure is particularly easily formed.

  In the present invention, it is important that the ratio of single fibers having a PPS single fiber diameter of 1500 to 5000 nm is 0 to 5% in the nanofiber aggregate. Here, the ratio of single fibers having a single fiber diameter of 1500 to 5000 nm can be determined as follows. First, as with the average diameter, the diameter in terms of a circle is obtained on the basis of the cross-sectional area of the fiber. And the ratio of the area of the whole single fiber of diameter 1500-5000 nm with respect to the area of 300 or more of the PPS nanofiber single fibers random extracted here, in this invention, the diameter of the single fiber whose PPS single fiber is 1500-5000 nm The ratio of

  Here, the capture efficiency of the fine particles can be improved by reducing the ratio of coarse nanofibers having a diameter of 1500 to 5000 nm. The ratio of coarse nanofibers having a diameter of 1500 to 5000 nm is preferably 2% or less, more preferably 0%. Further, it is preferable to lower the lower limit value of the coarse nanofiber, and as the coarse nanofiber, the ratio of the single fiber having a diameter of 500 to 5000 nm is preferably 0 to 5%, more preferably 2% or less, and further preferably 0%. It is. Furthermore, as a coarse nanofiber, it is preferable that the ratio of the single fiber with a diameter of 200-5000 nm is 0-5%, More preferably, it is 2% or less, More preferably, it is 0%. Furthermore, as a coarse nanofiber, it is preferable that the ratio of the single fiber with a diameter of 100-5000 nm is 0-5%, More preferably, it is 2% or less, More preferably, it is 0%. In particular, the nonwoven fabric can be densified by reducing the ratio of fibers of 200 nm or more.

  The PPS nanofiber used in the present invention has a large L / D, which is the ratio of the fiber length (L) to the fiber diameter (D), and the L / D is preferably 50 or more. Thereby, the form retention power of the dry nonwoven fabric is improved, and the mechanical properties of the dry nonwoven fabric can be improved.

  In the present invention, it is important for the PPS nanofiber to have a mixture of a part forming a bundle structure and a part forming a dispersion structure. In the present invention, the portion forming the bundle structure means a portion where the PPS nanofibers are closely adhered to each other in the fiber axis direction to form a bundle structure and densely aggregated, A portion in which fibers are oriented and aggregated over a width of 1 μm or more and is independent from the surroundings is called a portion forming a bundle structure. On the other hand, the part forming the dispersed structure refers to a part in which PPS nanofibers are aggregated with single fibers or aggregates of two or several pieces facing different directions. Further, when paying attention to the orientation of the single PPS nanofibers, it can be said that the portion where the orientations of the single fibers are aligned is the bundle structure, and the portion where the orientation is disturbed is the dispersion structure.

  The dry nonwoven fabric of the present invention will be described in more detail with reference to the drawings. FIG. 1 shows an example of a dry nonwoven fabric composed of 100% PPS nanofibers of the present invention, but there is almost no large inter-fiber gap of 100 μm or more as in the conventional PPS dry nonwoven fabric, and the entire structure is dense. is doing. In addition, when the average diameter of the PPS nanofiber single fiber is 200 nm or less, there is almost no space between the PPS nanofibers. Therefore, ordinary PPS fibers as described in JP-A-2000-79308 are simply contracted or hot pressed. Thus, it is possible to form a dense layer having a much higher density than the dense layer obtained.

  A portion surrounded by a dotted line is a distributed structure, and a portion indicated by an arrow is a part of the bundle structure. The bundle structure has a fiber diameter as a bundle fiber of several μm to several tens of μm by agglomeration of many PPS nanofibers, forms a skeleton of the entire dry nonwoven fabric, and gives sufficient mechanical properties to the dry nonwoven fabric. Can do. In the bundle structure portion, the gap between the PPS nanofibers is small and densely aggregated at about 1 to several tens of nanometers, so that the fine particles are prevented from excessively entering the inside of the dry nonwoven fabric and have a clogging suppressing effect. it can. In addition, since the fine particles stop on the nonwoven fabric surface, it is easy to remove the fine particles from the nonwoven fabric surface, and it is also advantageous for a cleaning method (so-called backwashing) in which a jet stream or water flow is applied from the back of the filter, which is generally performed in filter cleaning. It is. In addition, the bundle cross section of the bundle structure portion can take various forms such as an elliptical shape, a crushed ribbon shape, and an indeterminate shape as well as a circular shape, but the bundle structure made of PPS nanofibers is like a ribbon shape. It is preferable to adopt a form that is crushed. Compared to the case where the bundle structure is circular, the PPS nanofibers can be densely aggregated in a planar shape, so that the gaps between the bundle structures can be filled, and the fine particles enter the dry nonwoven fabric more effectively. This is because it is advantageous for suppressing clogging. Furthermore, since a large hole of about several μm to about 100 μm can be formed around the bundle structure, it is possible to suppress excessive increase in pressure loss due to easy passage of gas and liquid.

  On the other hand, the dispersion structure portion is formed by disturbing the bundle structure, and is dispersed to fibers having a fiber diameter of several tens to several hundreds of nanometers in which a plurality of PPS nanofibers are aggregated. A sheet-like structure is formed. For this reason, although there is a distribution in the gaps between the PPS nanofibers in the dispersed structure portion, if it is large, it may be 1 μm to several μm as shown in FIG. The structure may be suitable for capturing. Further, as shown in FIG. 3, when the gap between PPS nanofibers is as small as several tens to several hundreds nm, it is suitable for capturing finer fine particles. Furthermore, since the space | gap between nanofibers is small, it can prevent that microparticles | fine-particles penetrate | invade into a dry-type nonwoven fabric too much, and can bear a clogging suppression effect. In addition, since the fine particles stop on the nonwoven fabric surface, it is easy to remove the fine particles from the nonwoven fabric surface, and it is also advantageous for a cleaning method (so-called backwashing) in which a jet stream or water flow is applied from the back of the filter, which is generally performed in filter cleaning. It is.

  As described above, in the present invention, the dispersion structure portion can be mainly responsible for improving the trapping efficiency of the fine particles. On the other hand, the bundle structure portion forms a skeleton of the entire dry nonwoven fabric and can impart sufficient mechanical properties. Moreover, since PPS nanofibers are densely aggregated compared with the conventional PPS dry-type nonwoven fabric in any part, it can prevent that microparticles | fine-particles penetrate | invade excessively into a dry-type nonwoven fabric, and can bear a clogging suppression effect.

  In this way, in the present invention, the PPS nanofiber can have a function as an excellent filter that has never been obtained by collaborating the part having the bundle structure and the part having the dispersion structure. is there.

  Further, from the viewpoint of improving the trapping efficiency of the fine particles, the abundance ratio between the bundle structure and the dispersion structure on the dry nonwoven fabric surface is important, and it is important that the dispersion structure is 5 to 95% of the dry nonwoven fabric surface. Thereby, it is possible to achieve the above-described improvement in fine particle capturing property, suppression of clogging, and improvement in the mechanical strength of the dry nonwoven fabric. Here, if the dispersion structure is 10% or more of the dry nonwoven fabric surface, it is preferable because the fine particle capturing ability can be further improved. On the other hand, if the dispersion structure is 90% or less, the mechanical properties and form stability of the dry nonwoven fabric can be improved, so that it can be used under more severe conditions.

  Here, the proportion of the dispersed structure in the dry nonwoven fabric surface can be determined as follows. First, the surface of the dry nonwoven fabric is randomly photographed with a scanning electron microscope (SEM) at a magnification of several hundred to several thousand times (FIG. 1 is 200 times, and FIGS. 2, 3 are 2000 times). Then, the area of the dispersed structure portion is obtained from this photograph, and the ratio to the area of the dry nonwoven fabric surface on the photograph is obtained. By performing this at three or more locations and averaging, the ratio of the dispersed structure to the dry nonwoven fabric surface can be determined.

The basis weight of the dry nonwoven fabric of the present invention can be appropriately selected depending on the use, but when used for a bag filter or the like, it is preferably 200 to 600 g / m ² in order to obtain mechanical properties and form stability, When used for electrical insulation applications such as filters, battery separators and motor separators, it is preferably ²⁰ to 200 g / m ² . Further, the thickness of the dry nonwoven fabric can be appropriately selected depending on the use, but when used for a bag filter or the like, it is preferably 0.1 to 2 cm in order to obtain mechanical properties and shape stability, When used for electrical insulation applications such as battery separators and motor separators, the thickness is preferably 0.01 to 0.1 cm.

  The tensile strength of the dry nonwoven fabric of the present invention is preferably 1 N / cm or more from the viewpoint of processability to the filter unit, handleability, durability, and pressure resistance when used as a bag filter. The tensile strength is preferably 20 N / cm or more.

  Further, the tear strength of the dry nonwoven fabric of the present invention is preferably 1 N or more from the viewpoint of processability to the filter unit, handleability, durability, and pressure resistance when used as a bag filter. The tear is preferably 4N or more.

  In addition, fibers other than PPS nanofibers may be mixed in the dry nonwoven fabric of the present invention from the viewpoint of further improving heat resistance and mechanical properties. For example, wholly aromatic fibers are generally preferred because of their high heat resistance and mechanical properties. In particular, metaphenylene terephthalamide fiber, which is one of wholly aromatic aramid fibers, is preferable from the viewpoint of flame retardancy, and paraphenylene terephthalamide fiber, which is also one of wholly aromatic aramid fibers, from the viewpoint of special mechanical properties. And polybenzoxazole fibers which are wholly aromatic polymers are preferred. In addition, since the fully aromatic aramid fiber may be inferior in dimensional stability due to moisture absorption, liquid crystal polyester fiber having almost no dimensional change due to moisture absorption can be suitably used. Furthermore, it is also preferable to mix cellulose fibers and the like in order to provide not only heat resistance but also a filter function by adsorption.

  In addition, there are no particular restrictions on the form of mixing, such as blending with PPS nanofiber short fibers, or laminating a PPS nanofiber dry nonwoven fabric and a fabric or sheet made of other fibers. In the case of lamination, not only a woven or knitted fabric, a dry nonwoven fabric, or a wet nonwoven fabric, but also a film or a board may be laminated. In the case of mainly improving the heat resistance of the entire dry nonwoven fabric, blended cotton is preferable, and in the case where the heat resistance of only one surface of the dry nonwoven fabric is improved, lamination is preferable. Moreover, when mainly improving the mechanical properties of the dry nonwoven fabric, lamination is preferable.

  Moreover, from the viewpoint of improving the functionality of the dry nonwoven fabric, functional materials other than fibers may be mixed in the dry nonwoven fabric of the present invention. For example, when the dry nonwoven fabric of the present invention is used for a liquid filter or the like, various adsorbents can be carried on the dry nonwoven fabric. Moreover, the trapped fine particles and compounds can be decomposed by supporting various catalysts on the dry nonwoven fabric of the present invention. However, since PPS generally has not so high light resistance, a thermal catalyst is preferable to a photocatalyst. When using a photocatalyst, it is preferable to use a photocatalyst having a wavelength of 400 nm or more. In addition to the adsorbent and catalyst, it is of course possible to include a conductive substance, a smoothing agent, and the like. Moreover, it is suitable for electrode members, such as a fuel cell and a solar cell, to carry a conductive substance. Examples of the conductive substance include carbon materials such as carbon black, fullerene and carbon nanotubes, metal compound materials such as copper iodide, and organic materials such as conductive polymers. Furthermore, by using a photosensitizer typified by a bipyridyl ruthenium complex and the above conductive nonwoven fabric, it can be used for solar cells having excellent light energy conversion efficiency or light energy conversion devices that mimic a photosynthesis model. Can do.

  Although the manufacturing method of the dry-type nonwoven fabric which consists of PPS nanofiber of this invention is not specifically limited, For example, the following manufacturing methods can be used suitably. That is, first, a polymer alloy fiber having PPS as an island and an easily soluble polymer as a sea is obtained, and after making this into a dry nonwoven fabric, the easily soluble polymer as a sea is removed to remove the dry type composed of the PPS nanofibers of the present invention. A nonwoven fabric can be obtained.

  First, it is important to obtain a polymer alloy fiber using PPS as an island and an easily soluble polymer as a sea. Here, in the cross section of the polymer alloy fiber, the average diameter of PPS which is an island is 1 to 1500 nm, and the diameter is 1500. It is important that the ratio of the island of ˜5000 nm is 0 to 5% with respect to the area of the whole island. Since the diameter of the island has a great influence on the diameter of the nanofiber, the average diameter of the island is preferably 900 nm or less, more preferably 500 nm or less, still more preferably 200 nm or less, and most preferably 100 nm or less. Similarly, it is important to reduce the ratio of coarse islands having a diameter of 1500 to 5000 nm, and the ratio of coarse islands having a diameter of 1500 to 5000 nm is preferably 2% or less, more preferably 0%. Further, it is preferable to lower the lower limit value of the coarse island, and as the coarse island, the ratio of the islands having a diameter of 500 to 5000 nm is preferably 0 to 5%, more preferably 2% or less, and further preferably 0%. Furthermore, as a coarse island, the ratio of islands having a diameter of 200 to 5000 nm is preferably 0 to 5%, more preferably 2% or less, and still more preferably 0%. Furthermore, as a coarse island, the ratio of islands having a diameter of 100 to 5000 nm is preferably 0 to 5%, more preferably 2% or less, and still more preferably 0%.

  As described above, it is important to disperse PPS as finely and uniformly as possible in the sea polymer. For this reason, kneading of polymers is extremely important, and in the present invention, it is preferable to highly knead by a kneading extruder, a static kneader or the like. It should be noted that the simple chip blend described in Japanese Patent Application Laid-Open No. 61-252315 or the like is insufficient in kneading, so that it is difficult to finely and uniformly disperse islands as in the present invention.

  Specific guidelines for kneading depend on the sea polymer to be combined with PPS, but when using a kneading extruder, it is preferable to use a biaxial extrusion kneader, and when using a static kneader, The number of divisions is preferably 1 million or more. Moreover, in order to avoid blend spots and fluctuations in the blend ratio over time, it is preferable to measure each polymer independently and supply the polymers to the kneading apparatus independently. At this time, the polymer may be supplied separately as pellets, or may be supplied separately in a molten state. Two or more kinds of polymers may be supplied to the root of the extrusion kneader, or may be a side feed that supplies one component from the middle of the extrusion kneader.

  When a twin screw extrusion kneader is used as the kneading apparatus, it is preferable to achieve both high kneading and suppression of the polymer residence time. The screw is composed of a feeding part and a kneading part, but it is preferable that the kneading part has a length of 20% or more of the effective length of the screw so that high kneading can be achieved. Moreover, excessive shear stress can be avoided and the residence time can be shortened by setting the length of the kneading part to 40% or less of the effective screw length. Further, the kneading part is positioned as close as possible to the discharge side of the twin-screw extruder, so that the residence time after kneading can be shortened and re-aggregation of the island polymer can be suppressed. In addition, when strengthening kneading, it is possible to provide a screw having a backflow function for sending the polymer in the reverse direction in an extrusion kneader.

Further, in order to finely disperse the island PPS with an island diameter of several tens of nanometers, the combination of the polymers is also important, and it is preferable to select a polymer having compatibility with PPS as much as possible. Also, since PPS has a high melting point of about 280 ° C., the sea polymer is preferably one that has a small thermal decomposition even at 300 ° C. or higher, and a polymer that has a weight loss rate of 5% or less when held at 300 ° C. for 5 minutes is preferable. Furthermore, the melt viscosity of the sea polymer is also important. As described above, since PPS is a high melting point polymer, the kneading temperature and the spinning temperature are 300 ° C. or higher. Therefore, it is preferable to maintain a sufficient melt viscosity even at this temperature. More specifically, when a polymer having a melt viscosity of 150 Pa · s or higher at 300 ° C. and 1216 sec ⁻¹ is used as a sea polymer, sufficient shear can be applied to the island PPS, and the island PPS can be refined and uniformly dispersed. Is preferred for. Conversely, if the viscosity of the PPS forming the islands is set as low as possible, the island polymer is likely to be deformed by shearing force, and therefore, the island polymer is likely to be finely dispersed, which is preferable from the viewpoint of nanofiber formation. More specifically, the melt viscosity of PPS at 300 ° C. and 1216 sec ⁻¹ is preferably 200 Pa · s or less.

  In addition, when seawater is removed from polymer alloy fibers to form PPS nanofibers, the environmental impact can be reduced by using an aqueous solution as the seawater-removing solvent. Therefore, seawater polymers such as polyester and polycarbonate are hydrolyzed. And hot water-soluble polymers such as polyalkylene glycol, polyvinyl alcohol and derivatives thereof are preferred. Patent Document 1 describes that PPS nanofibers can be obtained by eluting nylon 6 from polymer alloy fibers using PPS as an island and nylon 6 as the sea using formic acid. Formic acid has a boiling point. It is a very difficult solvent to handle because of its low vapor pressure and high vapor pressure, and high risk of explosion. For this reason, even if PPS nanofibers can be obtained in beaker level experiments as described in Patent Document 1, an attempt is made to obtain a sufficient amount of PPS nanofiber short fibers for producing a dry nonwoven fabric. Therefore, it is necessary to newly introduce a considerably large solvent recovery / treatment facility, which not only increases the cost but also increases the environmental load, and it is not easy to actually obtain a dry nonwoven fabric made of PPS nanofibers.

  From the above viewpoint, it is particularly preferable to use high-viscosity polyethylene terephthalate capable of alkaline hydrolysis for the sea polymer.

  In addition, an appropriate compatibilizing agent can be used to make the dispersion diameter of PPS fine. For example, when a silane coupling agent type or epoxy type is used, the island diameter of the PPS can be set to 50 nm or less.

  When spinning the PPS polymer alloy used in the present invention, the cooling condition of the yarn is also important. Since the polymer alloy is a very unstable molten fluid, it is preferable to quickly cool and solidify after discharging from the die. For this reason, it is preferable that the distance from a nozzle | cap | die to the cooling start shall be 1-15 cm. Here, the start of cooling means a position where positive cooling of the yarn is started, but in the actual melt spinning apparatus, it is replaced with this at the upper end of the chimney.

  Hereinafter, a method for producing a dry nonwoven fabric by a needle punch method or a water jet punch method will be described first.

The spun polymer alloy fiber is preferably subjected to stretching and heat treatment, but the preheating temperature during stretching is preferably equal to or higher than the glass transition temperature (T _g ) of the PPS, so that the yarn unevenness can be reduced. .

  A polymer alloy fiber containing PPS thus obtained can be combined with a tow. For example, when the polymer alloy fiber tow fineness is 600,000 dtex, the spinning is performed using a spinning machine used for so-called staple fibers, and the yarn is formed into a thick fineness of 400 dtex or more at the spinning stage, and the yarn is combined. It is preferable to form tow from the viewpoint of improving productivity. However, at this time, it is preferable from the viewpoints of productivity improvement and spinnability improvement that the number of nozzle holes is 200 or more and the single fiber fineness of the polymer alloy is 1 to 10 dtex. In addition, when the number of holes in the base is 200 or more, the diameter of the base is 140 mm or more, which is larger than the diameter of the base used in so-called long fibers used for woven and knitted fabrics. Moreover, in the spinning of the present invention, rapid cooling is preferable. The temperature distribution of may increase. For this reason, it is preferable to employ a spinning spinning temperature lower than the spinning temperature employed in normal PPS in order to suppress yarn breakage and fluctuations in yarn physical properties due to differences in polymer viscosity depending on the base hole position. As a result, the difference between the atmospheric temperature and the spinning temperature is reduced, and variations due to the cap hole position can be suppressed. In addition, when a polymer with different chargeability from PPS is used as the sea polymer, there are cases where static electricity is likely to be generated in the polymer alloy fiber, but the tow convergence is improved, and the process stability at the time of combining and drawing is improved. Therefore, it is preferable to use products such as fatty acid esters and polyethers as the main component of the process oil.

  Moreover, when the toe fineness which consists of a polymer alloy fiber exceeds 10,000 dtex, it is preferable to set it as steam extending | stretching rather than the dry heat extending | stretching currently used with the long fiber. This is due to heat transfer between fibers in dry heat drawing, and uniform heat transfer to the vicinity of the center in the tow cross section may be insufficient, whereas in steam drawing, high-temperature steam fills the gaps between fibers. Therefore, heat transfer efficiency is high, heat can be uniformly transmitted to the vicinity of the center of the tow, and the tow can be stretched uniformly.

  Then, the drawn tow is guided to a crimper, subjected to mechanical crimping, and cut into fiber lengths of 31 to 70 mm to obtain raw cotton made of polymer alloy fibers. Here, by setting the number of crimps of the raw cotton to 5-40 crests / 25 mm, not only the card passing property, which is the next process, is improved, but also the openability of the raw cotton here is improved, and needle punching and water It is preferable because the mechanical properties and form stability of the dry nonwoven fabric can be improved by improving the entanglement property of the short fibers in the jet punch.

  In addition, it is also possible in principle to obtain raw cotton by applying false twisting to a polymer alloy fiber having a total fineness of about 100 dtex, applying crimps, and then cutting and cutting to obtain raw cotton. It is preferable to adopt the above-described staple fiber system.

  After blending the polymer alloy cotton thus obtained as necessary, a cotton with a desired basis weight is obtained by laminating the cotton with a cross-wrap weber. At this time, it is also possible to laminate a web made of polymer alloy cotton and a web made of other fibers. Moreover, it is also possible to laminate | stack a web on another woven / knitted fabric, a nonwoven fabric, and a sheet | seat.

Next, needle punching or water jet punching is performed, and the short fibers of the web are entangled to form a nonwoven fabric. At this time, it is preferable that the number of punches of the needle punch is 100 / cm ² or more because an apparent density and mechanical properties sufficient as a nonwoven fabric can be obtained. Moreover, it is preferable by setting it to 2500 pieces / cm < ² > or less because the through-hole on the nonwoven fabric surface by an excessive punch can be suppressed. In addition, the water pressure at the time of the water jet punch is 5 kg / cm ² or more to obtain sufficient short fiber entanglement, and by setting it to 100 kg / cm ² or less, it is possible to prevent excessive damage of the nonwoven fabric, preferable. In particular, when the fiber length is 31 to 70 mm, the water pressure is preferably 50 to 100 kg / cm ² . In addition, it is preferable that the water jet nozzles be arranged at a pitch of 1 mm or less because uniform punching is possible.

  In this way, a dry nonwoven fabric made of polymer alloy fibers can be obtained by a needle punch method or a water jet punch method.

  Next, a method for producing a dry nonwoven fabric by a spunbond method or a melt blow method will be described. In the spunbond method, as described above, a dry nonwoven fabric can be obtained by collecting the polymer alloy fibers discharged from the die at a high speed with an air ejector and collecting the spread fibers with a collection device installed below. Here, the take-up speed can be adjusted by the air pressure of the high-pressure airflow introduced into the air ejector, but the take-up speed can be 2000 to 6000 m / min. From the viewpoint of improving the thermal dimensional stability of the fiber, it is preferable to perform orientation crystallization in the spinning process. The specific take-up speed is preferably 2500 m / min or more, although it depends on the viscosity of the polymer alloy. Further, from the viewpoint of suppressing yarn breakage during spinning, the take-up speed is preferably 5000 m / min or less. It is also possible to cause the yarn to collide with the opening plate installed below the air ejector and to open it with electrostatic force.

On the other hand, in the melt blow method, a high-pressure air stream is introduced into the base, and a polymer melt is placed on the air stream and blown away from the base at once. This is a method suitable for easily obtaining thin fibers, and is an effective method for reducing the thickness of the PPS nanofiber bundle structure of the present invention. For both the spun bond method and the melt blow method, setting the polymer melt viscosity to be lower than that of normal spinning is advantageous in terms of spinnability and ultrafine yarn. Therefore, the melt viscosity at 300 ° C. and 1216 sec ⁻¹ of the polymer used in the sea is preferably less than 150 Pa · s. Although this is a disadvantageous direction for PPS miniaturization, the melt blow method has a much larger draft ratio than ordinary spinning, and therefore PPS miniaturization can be achieved here.

  Next, a method for obtaining a dry nonwoven fabric made of PPS nanofibers by removing the sea polymer from the dry nonwoven fabric made of polymer alloy fibers thus obtained will be described. The sea polymer may be dissolved in a solvent for sea removal, or it may be decomposed to oligomers or monomers by hydrolysis or the like, and sea removal may be performed, but the latter is preferable because of high uniformity in sea removal. It is preferable to use an alkaline aqueous solution as the solvent used here because the risk of explosion and corrosion is small. Further, when the dry nonwoven fabric is made of only PPS nanofibers after sea removal, the form stability of the dry nonwoven fabric tends to be lowered, but in this state, a strong force or a large deformation is applied to the dry nonwoven fabric in a liquid absorbing state such as a squeeze. Then, the form of the dry nonwoven fabric may be deformed. For this reason, when passing through a process in which a strong force or large deformation is applied to the dry nonwoven fabric in the liquid absorption state, by laminating other woven or knitted fabric, nonwoven fabric, or sheet on the dry nonwoven fabric composed of polymer alloy fibers as a precursor. It is preferable to form a support. This support may be used as it is, or may be removed by shaving as necessary.

  In the present invention, it is important that the part where the PPS nanofibers form a bundle structure and the part where the dispersion structure is formed are mixed, but in order to form the dispersion structure, the PPS nanofiber has an affinity with PPS. PPS nanofibers can be partially opened from a bundle structure by putting a dry nonwoven fabric composed of PPS nanofibers in a good solvent and applying a sag treatment, a shaking treatment, an ultrasonic treatment, or the like. Here, the solvent having a good affinity for PPS is preferably a solvent having a phenyl group such as phenol, but is not particularly limited as long as the object of the present application can be achieved. In addition, it is also effective to form a dispersion structure by subjecting a cyclic nonwoven fabric made of PPS nanofibers to water, surfactant, ultrasonic treatment, or the like in water containing a surfactant instead of a good solvent. It is also effective to form a dispersed structure by subjecting a dry nonwoven fabric made of polymer alloy fibers to buffing treatment and then eluting the sea polymer.

  The above method is also effective for making the bundle structure into a collapsed shape such as a ribbon. Furthermore, the drying method after performing such treatment is also important from the viewpoint of form control. After performing the above treatment, the dry nonwoven fabric made of PPS nanofibers is squeezed with a mangle or the like and dried while holding the nonwoven fabric surface. As a result, the bundle structure can be easily crushed into a ribbon shape, whereby a dense layer made of unprecedented PPS nanofibers can be formed.

Furthermore, in the present invention, the apparent density, denseness, thickness, and the like of the nonwoven fabric can be appropriately selected by applying a calender roll or the like to the dry nonwoven fabric composed of the PPS nanofibers thus obtained. Conventionally, since PPS fibers are not easily crushed even when a calendar roll is applied, it is not easy to adjust the apparent density, denseness, thickness, etc., but in the present invention, the apparent heat deformation temperature is obtained by converting the PPS fibers into nanofibers. It is also characterized in that it may be lower than that of conventional PPS fibers, and since single fibers are very thin and easily fill the gaps, they are much more easily crushed and densified than conventional PPS fibers. Specifically, a heat press temperature such as a calender roll can employ 180 to 260 ° C., and a linear pressure of 1 to 10 ton / m can be employed. In particular, when a paper-like material is obtained by densifying a dry nonwoven fabric, the hot press temperature is preferably 200 ° C. or higher and the pressure is 15 kg / cm ² or higher.

  The dry nonwoven fabric composed of the PPS nanofibers of the present invention can be suitably used for bag filters, liquid filters, electrical insulating materials, battery members, and the like. Furthermore, a dry nonwoven fabric made of PPS can be oxidized to form a nonwoven fabric made of polyphenylene sulfide oxide (hereinafter abbreviated as PPSO). PPSO has a much higher heat resistance than PPS and is a flame retardant material. However, conventional PPSO paper has a problem that there are many gaps in the paper and the dielectric breakdown tends to occur. For this reason, an attempt was made to fill this gap even when a calendar roll was applied, but the gap could not be filled sufficiently. However, if an overwhelmingly dense PPS nonwoven fabric of the present invention is oxidized, a dense PPSO nonwoven fabric that has never been obtained can be obtained, and sufficient dielectric breakdown characteristics can be exhibited. Thereby, it can use suitably for the use for which higher heat resistance is requested | required, and the use for which a flame retardance is requested | required. More specifically, an insulating material for a motor having a large output can be used.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the measuring method in an Example used the following method.

A. Polymer melt viscosity The polymer melt viscosity was measured by Toyo Seiki Capillograph 1B. The polymer storage time from sample introduction to measurement start was 10 minutes.

B. Melting | fusing point The peak top temperature which shows melting | fusing of a polymer by 2nd run using Perkin Elmaer DSC-7 was made into melting | fusing point of a polymer. The temperature rising rate at this time was 16 ° C./min, and the sample amount was 10 mg.

C. Worcester spots of polymer alloy fibers (U%)
Measurement was performed in the normal mode at a yarn feeding speed of 200 m / min using a USTER TESTER 4 manufactured by Zerbegger Worcester.

D. Fiber cross-sectional observation by TEM Ultra-thin sections were cut in the cross-sectional direction of the fiber, and the fiber cross-section was observed with a transmission electron microscope (TEM). Metal staining was applied as needed.

TEM apparatus: H-7100FA type manufactured by Hitachi, Ltd. Average diameter of single fibers of nanofibers Single-fiber diameters are calculated in terms of circles using a TEM image of the cross-sectional image of the fiber using image processing software (WINROOF), and the diameter of 300 single fibers randomly selected is the cross-sectional area. The average diameter was calculated from the average on the basis. More specifically, when the cross-sectional area of each single fiber is S _i , the average cross-sectional area (S _av ) of the single fiber is obtained from ΣS _i (i = 1 to n) / n, and the average diameter (D _av ) was determined by D _av = (4S _av / π) ^1/2 .

F. Using single fiber diameter data of the fiber ratios the TEM observation, the area of the single fiber of each nanofiber and _{S i} is the sum and the total area _{(S 1 + S 2 + ...} + S n). The frequency (number) of nanofibers having the same single fiber diameter was counted, and the product divided by the total area was defined as the fiber ratio of the single fiber. At this time, 300 nanofibers or more randomly extracted in the same cross section were used for calculation.

G. SEM observation A platinum-palladium alloy was deposited on the fiber, and the side surface of the fiber was observed with a scanning electron microscope.

SEM apparatus: Hitachi S-4000 type Proportion of the portion forming the dispersion structure on the dry nonwoven fabric surface First, the dry nonwoven fabric surface is randomly photographed with a scanning electron microscope (SEM) at a magnification of 200 times. Then, the area of the dispersed structure portion is obtained from this photograph, and the ratio to the area of the dry nonwoven fabric surface on the photograph is obtained. This was performed at three or more locations and averaged to determine the ratio of the dispersed structure to the dry nonwoven fabric surface.

I. Mechanical properties of the fiber The mechanical properties of the fiber were determined as follows. At room temperature (25 ° C.), an initial sample length = 200 mm, a pulling rate = 200 mm / min, and a load-elongation curve was obtained under the conditions shown in JIS L1013. Next, the load value at break was divided by the initial fineness, which was used as the strength, and the elongation at break was divided by the initial sample length to obtain a strong elongation curve.

J. et al. The number of crimps of the fiber was sampled 50 mm, the number of peaks and valleys between 25 mm in the vicinity of the center was counted, and the number of crimps was determined by halving this. Actually, the average value of n = 5 was used as the number of crimps of the fiber.

K. The basis weight, thickness and apparent density of the dry nonwoven fabric The basis weight of the nonwoven fabric was measured according to JIS L1096 8.4.2 (1999), the thickness was then measured, and the average value of the apparent density obtained therefrom was used as the apparent density. The thickness was measured using a dial thickness gauge (manufactured by Ozaki Mfg. Co., Ltd., trade name “Peacock H”), 10 samples were measured, and the average value was used.

L. Tensile strength of dry nonwoven fabric JIS L1096 8.12.1 (1999), width 5cm, length 2 from nonwoven fabric
A sample of 0 cm was taken and measured by stretching at a tensile speed of 10 cm / min with a constant speed extension type tensile tester at a grip interval of 10 cm. From the obtained value, the load per 1 cm width was defined as the tensile strength (unit: N / cm).

M.M. Tear strength of dry nonwoven fabrics The tear strength of nonwoven fabrics is determined by D method (JIS L 1096 8.15.1 (1999)).
Measured based on the pendulum method. N. Weight loss rate of polymer TG / DTA6200 manufactured by Seiko Instruments Inc. was used to measure the weight loss rate when heated from room temperature to 300 ° C at 10 ° C / min in a nitrogen atmosphere and then held at 300 ° C for 5 minutes. did.

Reference example 1
Melt viscosity 280Pa · s (300 ℃, 1216sec -1) 80 wt% of PET of melt viscosity 160Pa · s (300 ℃, 1216sec -1) as 20% by weight of PPS, a biaxial extrusion kneader under the following conditions Used for melt kneading. Here, the PPS used was a linear type and the molecular chain terminal was replaced with calcium ions. Further, the weight reduction rate when the PET used here was held at 300 ° C. for 5 minutes was 0.9%.

Screw L / D = 45
The kneading part length is 34% of the effective screw length
The kneading part was dispersed throughout the screw.

There are two backflow parts on the way. Polymer supply PPS and PET were weighed separately and supplied separately to the kneader.

Temperature 300 ° C
No vent The polymer alloy melt obtained here was introduced into a spinning machine as it was, and was spun. At this time, the polymer alloy melt was filtered with a metal nonwoven fabric having a spinning temperature of 315 ° C. and a limit filtration diameter of 15 μm, and then melt-spun from a die having a die surface temperature of 292 ° C. At this time, as the base, a nozzle having a discharge hole diameter of 0.6 mm provided with a measuring portion having a diameter of 0.3 mm above the discharge hole was used. And the discharge amount per single hole at this time was 1.1 g / min. Furthermore, the distance from the base lower surface to the cooling start point was 7.5 cm. The discharged yarn is cooled and solidified over 1 m with cooling air of 20 ° C., and after the process oil mainly composed of fatty acid ester is supplied, it is 1000 m / min through the non-heated first take-up roller and second take-up roller. It was wound up. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. This was subjected to a stretching heat treatment with the temperature of the first hot roller being 100 ° C. and the temperature of the second hot roller being 130 ° C. At this time, the draw ratio between the first hot roller and the second hot roller was 3.3 times. The obtained polymer alloy fiber exhibited excellent properties of 200 dtex, 96 filament, strength 4.4 cN / dtex, elongation 27%, U% = 1.3%. Moreover, the photograph which observed the cross section of the obtained polymer alloy fiber by TEM is shown in FIG. 4, and PPS was uniformly dispersed with a diameter of less than 100 nm as an island in PET which is a sea polymer. Moreover, when the circle-equivalent diameter of the island was analyzed by the image analysis software WINROOF, the average diameter of the island was 65 nm, and the ratio of islands having a diameter of 100 nm or more was 0%.

Reference example 2
Spinning and drawing were carried out in the same manner as in Reference Example 1 with a PET blending ratio of 60% by weight, a PPS blending ratio of 40% by weight, and a draw ratio of 3.1 times, and 215 dtex, 96 filaments, strength 4.4 cN / dtex. Excellent properties of 26% elongation and U% = 1.4% were exhibited. Moreover, when the cross section of the obtained polymer alloy fiber was observed by TEM, it was found that PPS was uniformly dispersed as islands in PET, which is a sea polymer. Further, when the circle-converted diameter of the island was analyzed with the image analysis software WINROOF, the average diameter of the island was 76 nm, the ratio of the island having a diameter of 100 nm or more was 7%, and the ratio of the island having a diameter of 150 nm or more was 0% (island diameter). The maximum value was 116 nm).

Reference example 3
Melt kneading was performed under the same conditions as in Reference Example 2 to obtain polymer alloy pellets once. The polymer alloy pellets were dried and then put into a spinning machine. The polymer alloy pellets were melted at 315 ° C. and led to a spin block with a spinning temperature of 315 ° C. The polymer alloy melt was filtered with a metal nonwoven fabric having a limit filtration diameter of 15 μm, and then melt-spun from a die having a die surface temperature of 292 ° C. At this time, as the base, a nozzle having a discharge hole diameter of 0.6 mm provided with a measuring portion having a diameter of 0.3 mm above the discharge hole was used. And the discharge amount per single hole at this time was 1.1 g / min. Furthermore, the distance from the base lower surface to the cooling start point was 10 cm. The discharged yarn is cooled and solidified over 1 m with a cooling air of 20 ° C., and after the process oil agent mainly composed of fatty acid ester is supplied, it is 1000 m / min through the non-heated first take-up roller and the second take-up roller. As a result, 20 yarns were collected and dropped into a yarn box. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. Furthermore, 40 of these were collected to form a tow composed of polymer alloy fibers, and steam stretching at 100 ° C. was performed. At this time, the draw ratio was 2.8 times. The obtained polymer alloy fiber tow was 770,000 dtex. Here, one yarn was taken out and steam-stretched under the above conditions and measured for physical properties. As a result, excellent properties such as a strength of 4.0 cN / dtex, an elongation of 35%, and U% = 1.5% were exhibited. Moreover, when the cross section of the obtained polymer alloy fiber was observed by TEM, it was found that PPS was uniformly dispersed as islands in PET, which is a sea polymer. Further, when the circle-converted diameter of the island was analyzed by the image analysis software WINROOF, the average diameter of the island was 80 nm, the ratio of the island having a diameter of 100 nm or more was 8%, and the ratio of the island having a diameter of 150 nm or more was 0%.

Reference example 4
PPS having a weight average molecular weight of 50,000 was melt-spun at a spinning temperature of 320 ° C. and spun at a take-up speed of 800 m / min to obtain an undrawn yarn, and these were combined. Then, steam stretching was performed at 100 ° C. and 3.2 times to obtain a PPS tow having a single fiber fineness of 1 dtex (single fiber diameter: 12 μm) and a tow fineness of 100,000 dtex.

Reference Example 5
In the same manner as in Reference Example 4, melt spinning, stretching and heat treatment were performed to obtain 250 dtex, 72 filament PPS long fibers.

Example 1
Twenty-five polymer alloy fibers obtained in Reference Example 1 were combined, and 20 were further combined to form a tow having a total fineness of 100,000 detex. This was passed through a crimper for staple fibers and subjected to mechanical crimping with a number of crimps of 16 peaks / 25 mm. This was cut into a fiber length of 51 mm to obtain a polymer alloy raw cotton. Furthermore, after making it open through a card | curd, the felt which consists of a polymer alloy fiber was produced with the cross wrap weber. The felt was subjected to needle punching at 1500 pieces / cm ² to obtain a dry nonwoven fabric made of polymer alloy fibers.

This was subjected to alkaline hydrolysis treatment, neutralization and washing with hot water using 98%, 10% by weight sodium hydroxide aqueous solution and “Mercerin PES” 5% owf as a weight loss accelerator, polymer alloy The sea polymer PET was completely removed from the fiber to obtain a dry nonwoven fabric composed of PPS nanofibers. Further, this dry nonwoven fabric was immersed in phenol, subjected to ultrasonic treatment for 20 minutes, squeezed with mangles, and then dried while pressing both sides with paper and applying a pressure of 0.5 kg / cm ² .

  Fibers were extracted from the obtained dry nonwoven fabric, and the cross section of the fibers was observed by TEM (FIG. 5). The average diameter was 60 nm, and the ratio of diameters of 100 nm or more was 0% (maximum diameter was 86 nm). In addition, although it seems that the nanofiber single fiber has adhere | attached in FIG. 5, this is considered because the contrast of TEM is hard to come out. Further, when the side surface of the PPS nanofiber was observed with an SEM, L could not be determined in the visual field range because the length (L) of the PPS nanofiber was large, but L / D was considered to be 50 or more. . Moreover, the thing whose L / D is 10 or less was zero. Furthermore, this PPS nanofiber was a thing which has no branch at all.

  Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric It was 60%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.

This dry nonwoven fabric had a basis weight of 150 g / m ² . Further, this was hot-pressed at 220 ° C. and 30 kg / cm ² . As a result, the thickness of the dry nonwoven fabric could be reduced to 0.3 mm. The thin dry nonwoven fabric obtained was suitable for a liquid filter.

Example 2
The polymer alloy fibers obtained in Reference Example 2 were combined in the same manner as in Example 1 to obtain 110,000 dtex tow. Further, after crimping with 14 crimps / 25 mm of crimps as in Example 1, a dry nonwoven fabric made of polymer alloy fibers was obtained by cutting and needle punching. Next, the PET was removed from the sea and dried in the same manner as in Example 1 to obtain a dry nonwoven fabric composed of PPS nanofibers. Then, after immersing in phenol as in Example 1, it was subjected to ultrasonic treatment and dried.

  Fibers were extracted from the obtained dry nonwoven fabric, and the cross section of the fibers was observed by TEM. The average diameter was 80 nm, the ratio of diameters of 100 nm or more was 8% (maximum diameter of 129 nm), and the ratio of diameters of 150 nm or more was 0%. It was. Further, when the side surface of the PPS nanofiber was observed with an SEM, L could not be determined in the visual field range because the length (L) of the PPS nanofiber was large, but L / D was considered to be 50 or more. It was. Moreover, the thing whose L / D is 10 or less was zero. Furthermore, this PPS nanofiber was a thing which has no branch at all.

  Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric It was 70%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.

This dry nonwoven fabric had a basis weight of 500 g / m ² and was suitable for a bag filter.

Example 3
The tow obtained in Reference Example 3 was crimped with a number of crimps of 14 peaks / 25 mm in the same manner as in Example 1, and then a dry nonwoven fabric made of polymer alloy fibers was obtained by cutting and needle punching. Next, the PET was removed from the sea and dried in the same manner as in Example 1 to obtain a dry nonwoven fabric composed of PPS nanofibers. Then, after immersing in phenol as in Example 1, it was subjected to ultrasonic treatment and dried.

  Fibers were extracted from the obtained dry nonwoven fabric, and the cross section of the fibers was observed by TEM. The average diameter was 80 nm, the ratio of diameters of 100 nm or more was 8% (maximum diameter of 129 nm), and the ratio of diameters of 150 nm or more was 0%. It was. Further, when the side surface of the PPS nanofiber was observed with an SEM, L of the PPS nanofiber was large and L could not be determined in the visual field range, but L / D was considered to be 50 or more. Moreover, the thing whose L / D is 10 or less was zero. Furthermore, this PPS nanofiber was a thing which has no branch at all.

  Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric It was 70%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.

This dry nonwoven fabric had a basis weight of 500 g / m ² and was suitable for a bag filter.

Comparative Example 1
A plain weave (weight per unit area: 150 g / m ² ) for a support was produced using the PPS long fibers obtained in Reference Example 5. Next, the PPS tow obtained in Reference Example 4 was crimped at 12 threads / 25 mm in the same manner as in Example 1 and cut into 51 mm to obtain PPS raw cotton. The PPS raw cotton was opened with a card and arranged in fibers, and then felt was produced with a cross-wrap weber. Then, the PPS plain weave for support prepared above was sandwiched with this PPS felt, and 200 needles / cm ² of needle punching was performed and integrated to obtain a dry nonwoven fabric having a basis weight of 400 g / cm ² . Furthermore, using a PPS raw cotton obtained by cutting the tow of Reference Example 4 separately, 200 needles / cm ² were needle punched to obtain a dry nonwoven fabric with a basis weight of 110 g / cm ² . This was passed through a calendar roll at 200 ° C. and 35 kg / cm ² to obtain a filter layer for a bag filter having a thickness of 0.25 mm. The dry nonwoven fabric having a basis weight of 400 g / cm ^{2 and} the filter layer for bag filter prepared previously were integrated with a needle punch. Further, this laminated nonwoven fabric was treated with hot air at 240 ° C., and contracted by about 5% both vertically and horizontally, and further passed through a calender roll at 200 ° C. and 35 kg / cm ² , and a bag filter having a basis weight of 570 g / cm ² and a thickness of 1.8 mm. A dry nonwoven fabric was obtained. When the surface of the filter layer was observed by SEM, the PPS fibers were somewhat dense. However, the fibers were much thicker than in the examples, so the inter-fiber voids were still large, and the densification was insufficient.

Example 4
The raw cotton made of the polymer alloy raw cotton obtained in Example 3 and the metaphenylene terephthalaramid fiber was mixed at a ratio of 4: 1. Using this, a dry nonwoven fabric made of polymer alloy fibers was obtained in the same manner as in Example 3. In the same manner as in Example 3, PET was removed from the sea and dried to obtain a dry nonwoven fabric composed of PPS nanofibers. Then, after immersing in phenol as in Example 1, it was subjected to ultrasonic treatment and dried.

  When PPS nanofibers were extracted from the obtained dry nonwoven fabric and the cross section of the fibers was observed by TEM, the average diameter was 81 nm, the ratio of diameters of 100 nm or more was 8% (maximum diameter was 130 nm), and the ratio of diameters of 150 nm or more was 0%. Met.

  Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric 40%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.

This dry nonwoven fabric had a basis weight of 500 g / m ² and was suitable for a bag filter. Furthermore, since flame-retardant metaphenylene terephthalamide fiber was mixed, the flame retardancy and heat resistance were further improved.

Example 5
The dry nonwoven fabric obtained in Example 3 and the PPS woven fabric prepared in Comparative Example 1 separately prepared were integrated with a needle punch. Thereafter, in the same manner as in Example 3, the PET was desealed and dried to obtain a dry nonwoven fabric composed of PPS nanofibers. Then, after immersing in phenol as in Example 1, it was subjected to ultrasonic treatment and dried.

  When PPS nanofibers were extracted from the obtained dry nonwoven fabric and the cross section of the fibers was observed by TEM, the average diameter was 80 nm, the ratio of diameters of 100 nm or more was 8% (maximum diameter was 129 nm), and the ratio of diameters of 150 nm or more was 0%. Met.

  Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric It was 70%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.

This dry nonwoven fabric had a basis weight of 570 g / m ² and was suitable for a bag filter. Since this laminated nonwoven fabric contains PPS woven fabric as a support, the shape stability during sea removal is good, and even when using a liquid dyeing machine, which is an alkali weight reduction device for ordinary weaving and knitting, during sea removal The form stability of was good. At this time, due to the stagnation effect by the liquid dyeing machine, 10% of the portion where the PPS nanofibers formed a dispersed structure existed even without phenol immersion. Furthermore, due to the effect of the support, the tensile strength of the entire dry nonwoven fabric was 80 N / cm, and the tear strength was 10 N, which was sufficient mechanical strength.

Example 6
Melting and kneading were carried out under the same conditions as in Reference Example 3 with 80 wt% of PET having a melt viscosity of 100 Pa · s and 20 wt% of PPS having a melt viscosity of 13 Pa · s to obtain once polymer alloy pellets. This was spun under the same conditions as in Reference Example 3, and the yarn was pulled at 4500 m / min with an air ejector installed 2 m below the base, and collided with a spread plate installed 1 m below the air ejector. The strips were opened and then collected on a conveyor net. Next, a spunbond nonwoven fabric made of polymer alloy fibers having a basis weight of 100 g / cm ² and a separately prepared cotton fabric having a basis weight of 135 g / cm ² were laminated by needle punching. Then, as in Example 1, it was desealed and dried to obtain a dry nonwoven fabric composed of PPS nanofibers laminated with a cotton fabric. Furthermore, after being immersed in phenol, it was subjected to ultrasonic treatment and dried.

  When PPS nanofibers were extracted from the obtained dry nonwoven fabric and the fiber cross section was observed by TEM, the average diameter was 75 nm, and the ratio of diameters of 100 nm or more was 0% (the maximum diameter was 98 nm).

Moreover, when the surface of this dry nonwoven fabric was observed by SEM, the portion where the PPS nanofibers formed a bundle structure and the portion where the dispersion structure was formed were observed, and the portion where the dispersion structure was formed was the surface of the dry nonwoven fabric It was 70%. In addition, the bundle structure portion was crushed in a ribbon shape in cross section, and the bundle structure overlapped to form a dense layer of PPS nanofibers. Further, depending on the place, there was a portion where a gap with a diameter of several tens to several hundreds μm was observed between the bundle structures.
Next, this laminated dry nonwoven fabric was hot-pressed at 200 ° C. and 35 kg / cm ² to obtain a dry nonwoven fabric composed of 100% PPS nanofibers in which the thickness of the PPS nanofiber portion was reduced to 0.2 mm. This was suitable for a liquid filter.

  Since this laminated nonwoven fabric contains cotton fabric as a support, it has good shape stability during sea removal, and even when using a liquid dyeing machine, which is an alkali weight reduction device for ordinary woven and knitted fabrics, The form stability was good. At this time, due to the stagnation effect by the liquid dyeing machine, 10% of the portion where the PPS nanofibers formed a dispersed structure existed even without phenol immersion. Furthermore, due to the effect of the support, the tensile strength of the entire dry nonwoven fabric was 80 N / cm, and the tear strength was 10 N, which was sufficient mechanical strength.

It is a figure which shows the surface state of the dry-type nonwoven fabric of this invention. It is a figure which shows the surface state of the dry-type nonwoven fabric of this invention. It is a figure which shows the surface state of the dry-type nonwoven fabric of this invention. It is a figure which shows the cross section of the polymer alloy fiber of the reference example 1. FIG. 1 is a cross-sectional view of a PPS nanofiber of Example 1. FIG.

Claims (6)

  A dry nonwoven fabric comprising polyphenylene sulfide nanofibers having an average single fiber diameter of 1 to 1500 nm and a ratio of single fibers having a diameter of 1500 to 5000 nm of 0 to 5%, and the polyphenylene sulfide nanofibers in the dry nonwoven fabric The portion where the bundle structure is formed and the portion where the dispersion structure is formed are mixed, and the portion where the polyphenylene sulfide nanofibers form the dispersion structure on the dry nonwoven fabric surface is 5 to 95 of the dry nonwoven fabric surface. % Dry nonwoven fabric.   The dry nonwoven fabric according to claim 1, wherein the average diameter of the single fibers of the polyphenylene sulfide nanofiber is 1 to 200 nm and the ratio of the single fibers having a diameter of 200 to 5000 nm is 0 to 5%.   The dry nonwoven fabric according to claim 1 or 2, wherein fibers other than polyphenylene sulfide nanofibers are mixed.   The dry nonwoven fabric according to claim 3, wherein the fibers other than the polyphenylene sulfide nanofibers are wholly aromatic fibers, liquid crystal polyester fibers, or cellulosic fibers.   The dry-type nonwoven fabric by which the other fabric or sheet | seat is laminated | stacked on the dry-type nonwoven fabric of any one of Claims 1-4.   The dry nonwoven fabric according to any one of claims 1 to 4, wherein other fibers are mixed with the polyphenylene sulfide nanofibers.