Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/10—Organic non-cellulose fibres
  • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4326—Condensation or reaction polymers
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
  • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
  • D04H1/43918—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres nonlinear fibres, e.g. crimped or coiled fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
  • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
  • D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to a polyphenylene sulfide fiber nonwoven fabric and a diaphragm containing the same.
• Polyphenylene sulfide has high heat resistance, chemical resistance, electrical insulation, and flame retardancy, as well as excellent mechanical properties and moldability. Widely used as a raw material. Polyphenylene sulfide fibers are also used for applications such as bag filters, papermaking canvases, electrical insulating papers, battery separators, and various diaphragms, taking advantage of these properties. In particular, for hydrogen production device diaphragms and fuel cell diaphragms, which are attracting attention as clean energy sources, and for diaphragm reinforcing materials, the characteristics of polyphenylene sulfide such as heat resistance and chemical resistance to high-concentration alkaline solutions, etc. Investigations have been made to combine the ion permeability and gas separation properties of non-woven fabric materials.
• a polyphenylene sulfide wet-laid nonwoven fabric composed of stretched polyphenylene sulfide fibers and unstretched polyphenylene sulfide fibers, which are binder fibers by thermocompression bonding, has been proposed (see, for example, Patent Document 1).
• Non-stretched polyphenylene sulfide fibers are plastically deformed by thermocompression bonding, and the stretched polyphenylene sulfide fibers are bonded together to form a nonwoven fabric having excellent tensile strength.
• a wet-laid nonwoven fabric made of a fine binder fiber with excellent adhesiveness, which is obtained by stretching unstretched polyphenylene sulfide fibers in an ethylene glycol bath at 110°C (see, for example, Patent Document 2).
• the nonwoven fabric has excellent tensile strength even when the fabric is thin.
• a wet-laid nonwoven fabric using a copolymerized polyphenylene sulfide fiber with low crystallinity as a papermaking binder has also been proposed (see, for example, Patent Document 3).
• a nonwoven fabric composed of a copolymer polyphenylene sulfide fiber and a polyphenylene sulfide fiber, and containing the copolymer polyphenylene sulfide fiber having a small diameter and a low heat shrinkage as a binder provides a thin non-woven fabric having excellent thermal dimensional stability.
• Patent Document 2 is advantageous for thinning the nonwoven fabric because it is composed of a single binder fiber with a small diameter stretched in an ethylene glycol bath at 110°C.
• the fibers tend not to fuse during heat calendering and retain their fiber shape, so the tear strength is not sufficient as described above.
• this method has the problem that the nonwoven fabric shrinks during the papermaking and drying process, causing drying wrinkles and swelling.
• Patent Document 3 since the fibers are made of copolymerized polyphenylene sulfide with a low melting point, the adhesion between the fibers is insufficient, and the tensile strength of the nonwoven fabric tends to decrease.
• An object of the present invention is to provide a polyphenylene sulfide fiber nonwoven fabric having both high tear strength and tensile strength, which is suitable for thinning and low basis weight, and a membrane containing the same.
• the present invention has the following configuration.
• copolymerized polyphenylene sulfide fiber (B) is a copolymerized polyphenylene sulfide fiber consisting of repeating units of p-phenylene sulfide units and m-phenylene sulfide units.
• the present invention it is possible to provide a polyphenylene sulfide fiber nonwoven fabric suitable for thinning and low basis weight. Moreover, the present invention can provide a polyphenylene sulfide fiber nonwoven fabric having excellent tear strength and tensile strength. Furthermore, it is possible to provide a polyphenylene sulfide fiber non-woven fabric that is less likely to break during the manufacturing process or break during subsequent processes. As a result, it is possible to provide a diaphragm with a reduced thickness and a lower basis weight.
• the repeating units are composed of p-phenylene sulfide units represented by the following general formula (1).
• the repeating unit is preferably 98.0 mol %, more preferably 99.0 mol % or more. Since the polyphenylene sulfide fiber (A) exhibits high fiber strength, the polyphenylene sulfide fused portion (C) fuses the fibers together to bear stress, resulting in a nonwoven fabric having high tensile strength.
• the mass % of the polyphenylene sulfide fiber (A) in the polyphenylene sulfide fiber nonwoven fabric is preferably 1 mass % or more, more preferably 2 mass % or more, from the viewpoint of improving the tensile strength. From the viewpoint of balance with tear strength, the content is preferably 80% by mass or less, more preferably 60% by mass or less.
• the presence of the polyphenylene sulfide fiber (A) in the present invention can be confirmed by microscopic infrared spectroscopic analysis described in Examples.
• the copolymerized polyphenylene sulfide fiber (B) in the present invention contains 4.0 mol% or more, preferably 5.0 mol% or more of at least one type of copolymerized unit other than p-phenylene sulfide.
• the tear strength can be improved by including the copolymerized polyphenylene sulfide fiber (B).
• the copolymer unit content is preferably 40.0 mol % or less, more preferably 30.0 mol % or less.
• copolymer units other than p-phenylene sulfide include aromatic sulfides such as triphenylene sulfide and biphenylene sulfide, and alkyl-substituted and halogen-substituted products thereof. It is preferably the m-phenylene sulfide shown.
• m-phenylene sulfide By containing m-phenylene sulfide as a copolymer unit, the melting point and / or crystallinity is lowered without impairing the characteristics of polyphenylene sulfide such as heat resistance and chemical resistance, so it is more effective at tearing. Crack propagation can be suppressed.
• the mass % of the polyphenylene sulfide fiber (B) in the polyphenylene sulfide fiber nonwoven fabric is preferably 1 mass % or more, more preferably 2 mass % or more, from the viewpoint of improving the tensile strength. From the viewpoint of balance with tear strength, the content is preferably 80% by mass or less, more preferably 60% by mass or less.
• the presence of the copolymerized polyphenylene sulfide fiber (B) containing m-phenylene sulfide in the nonwoven fabric can be confirmed by microscopic infrared spectroscopic analysis described in Examples.
• the copolymerized polyphenylene sulfide fiber (B) preferably contains 60.0 mol % or more and 96.0 mol % or less of the repeating units of p-phenylene sulfide units.
• the repeating unit of the p-phenylene sulfide unit is preferably 60.0 mol% or more, more preferably 70.0 mol% or more, so that the spinnability is good and the heat resistance and mechanical properties are excellent. It becomes polyphenylene sulfide fiber.
• the p-phenylene sulfide unit is preferably 96.0 mol% or less, more preferably 95.0 mol% or less, thereby lowering the crystallinity of the copolymerized polyphenylene sulfide and contributing to the improvement of the tear strength. It can be a copolymerized polyphenylene sulfide fiber.
• the m-phenylene sulfide unit which is a preferred copolymerization component, preferably accounts for 4.0 mol % or more and 40.0 mol % or less of the repeating units.
• the m-phenylene sulfide unit is more preferably 5.0 mol% or more, more preferably 6.0 mol% or more, so that the melting point and crystallinity of the copolymerized polyphenylene sulfide are lowered, and the crack growth during tearing described above is suppressed.
• a copolymerized polyphenylene sulfide fiber (B) having an excellent inhibitory effect can be obtained.
• the m-phenylene sulfide unit preferably 40.0 mol% or less, more preferably 30.0 mol% or less, excessive decrease in melting point and crystallinity is suppressed, and good heat resistance and mechanical properties are obtained.
• copolymerized polyphenylene sulfide fiber (B) having The mol % of the p-phenylene sulfide units and m-phenylene sulfide units of the copolymerized polyphenylene sulfide fiber (B) in the present invention is determined by the infrared microscopic analysis described in Examples.
• the copolymerized polyphenylene sulfide fiber (B) in the nonwoven fabric, easily deformable low-crystalline elements can be anisotropically scattered. As a result, crack growth due to tearing is suppressed, resulting in a nonwoven fabric with high tear strength.
• the cross-sectional shape of the polyphenylene sulfide fiber (A) and the copolymerized polyphenylene sulfide fiber (B) of the present invention is not limited at all, and may be a circular cross section, a multilobal cross section such as a triangular cross section, a flat cross section, or an S-shaped cross section. , a cross section, a hollow section, or any other shape.
• a circular cross section is preferred from the viewpoint of fiber dispersibility during papermaking.
• the copolymer polyphenylene sulfide fibers (B) are preferably partially fused to the extent that the effects of the present invention are not impaired. For example, if the surface is partially fused by heat calendering, etc., and the fiber shape remains while the fusion bondability with the surrounding fibers is also exhibited, the bonding area between the constituent fibers will increase, and the fibers will not come off. It can also contribute to reduction.
• copolymerized polyphenylene sulfide fiber (B) has been used as a binder fiber due to its low melting point. However, if this is the case, it becomes difficult to obtain high tensile strength due to insufficient adhesive strength as described above.
• the present invention has a polyphenylene sulfide fused part (C) as a binder.
• the p-phenylene sulfide unit is preferably 97.0 mol% or more, more preferably 98.0 mol% or more, in the polyphenylene sulfide fused portion (C) in order to form a strong bond. more preferably 99.0 mol % or more.
• the strength of the polyphenylene sulfide fused portion (C) can be increased, and breakage is less likely to occur when tensile stress is applied. becomes less likely to occur.
• the mol % of the p-phenylene sulfide unit in the polyphenylene sulfide fused portion (C) is determined by the infrared microscopic analysis described in Examples.
• the polyphenylene sulfide fused portion (C) in the present invention preferably has a shape in which at least part of the polyphenylene sulfide is formed into a film.
• the fused portion means a portion where, for example, when a binder fiber is used as a precursor, the shape of the fiber is lost and the fibers forming the nonwoven fabric are bonded together.
• the area ratio of the polyphenylene sulfide fused parts (C) in the polyphenylene sulfide fiber nonwoven fabric of the present invention is preferably 5 to 50%.
• the area ratio of the polyphenylene sulfide fusion-bonded portion (C) is preferably 5% or more, more preferably 10% or more.
• the polyphenylene sulfide fiber (A) and the copolymerized polyphenylene sulfide fiber (B) that exhibit excellent tensile strength in the nonwoven fabric are sufficiently present. , resulting in a nonwoven fabric with high tensile strength. Furthermore, it is possible to retain the softness and air permeability, which are characteristics of nonwoven fabrics.
• the area ratio of the polyphenylene sulfide fused portion (C) in the present invention uses a value measured by the method described in Examples by microscopic infrared spectroscopic analysis of the surface of the nonwoven fabric.
• the type of nonwoven fabric is not particularly limited, and examples include spunbond nonwoven fabrics, meltblown nonwoven fabrics, spunlace nonwoven fabrics, needle punch nonwoven fabrics, and papermaking nonwoven fabrics. easy and desirable.
• the polyphenylene sulfide fiber nonwoven fabric of the present invention has the most The melting point (Tm-L) defined as the peak top of the peak observed on the low temperature side is 240 to 270°C.
• Tm-L melting point
• the melting point (Tm ⁇ L) is 270° C. or less, preferably 265° C. or less, more preferably 260° C. or less.
• the copolymerized polyphenylene sulfide fibers (B) are not completely fused in the nonwoven fabric during heat calendering. , the decrease in tear strength can be suppressed.
• the melting point (Tm-L) to 240° C. or higher, preferably 243° C. or higher, more preferably 245° C.
• the copolymerized polyphenylene sulfide fibers are partially fused to suppress the fibers from falling out.
• heat resistance can be improved.
• Tm-L melting point of the polyphenylene sulfide fiber nonwoven fabric
• the polyphenylene sulfide fiber nonwoven fabric of the present invention preferably has a basis weight of 1.00 to 100 g/m 2 .
• a basis weight of 1.00 to 100 g/m 2 .
• the basis weight preferably 1.00 g/m 2 or more, more preferably 3.00 g/m 2 or more, and even more preferably 5.00 g/m 2 or more.
• breakage during the manufacturing process is less likely to occur, and the process Improves passability.
• the basis weight to preferably 100 g/m 2 or less, more preferably 80.0 g/m 2 or less, and even more preferably 60.0 g/m 2 or less
• the nonwoven fabric is lightweight and excellent in flexibility.
• the diaphragm can be made thin and low in basis weight.
• the basis weight of the nonwoven fabric in the present invention refers to the value measured by the method described in Examples.
• the thickness of the polyphenylene sulfide fiber nonwoven fabric of the present invention is preferably 5.00 to 300.00 ⁇ m.
• the thickness is preferably 5.00 ⁇ m or more, more preferably 8.00 ⁇ m or more, and even more preferably 10.00 ⁇ m or more, breakage during the manufacturing process is less likely to occur, and process passability is improved.
• the thickness is preferably 300.00 ⁇ m or less, more preferably 250.00 ⁇ m or less, and even more preferably 200.00 ⁇ m or less, the permeability to ions and the like when used as a diaphragm or the like is improved.
• the thickness of the nonwoven fabric in the present invention refers to the value measured by the method described in Examples.
• the tear strength of the polyphenylene sulfide fiber nonwoven fabric of the present invention is preferably 0.200 to 10.0N.
• the tear strength can be improved by increasing the proportion of the copolymerized polyphenylene sulfide fiber (B).
• the tear strength of the nonwoven fabric in the present invention refers to the value measured by the method described in Examples.
• the tensile strength of the polyphenylene sulfide fiber nonwoven fabric of the present invention is preferably 2.5 to 300.0 N/15 mm.
• the tensile strength is preferably 2.5 N/15 mm or more, more preferably 3.5 N/15 mm or more, and even more preferably 5.0 N/15 mm or more, breakage during the manufacturing process is less likely to occur.
• the nonwoven fabric is resistant to tearing even when a tensile stress is applied during subsequent processes or during use.
• the tensile strength to preferably 300.0 N/15 mm or less, more preferably 250.0 N/15 mm or less, and even more preferably 200.0 N/15 mm or less, the flexibility of the nonwoven fabric can be maintained, and the diaphragm It becomes a nonwoven fabric excellent in assembly property when used for such as.
• the polyphenylene sulfide fibers (A) having a high fiber strength are strongly bonded together by the polyphenylene sulfide fused portion (C), and the tensile strength can be improved.
• the fibers are less likely to come off, and the polyphenylene sulfide fiber (A) bears the stress, resulting in high tensile strength. It becomes a nonwoven fabric having strength.
• the tensile strength of the nonwoven fabric in this invention points out the value measured by the method as described in an Example.
• the square root ( ⁇ XY) of the product of the tear strength X (N) and the tensile strength Y (N/15 mm) is preferably 1.4 or more.
• ⁇ XY is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more, breakage or the like in the manufacturing process can be suppressed.
• tear strength and tensile strength it becomes a non-woven fabric that is difficult to tear even when it is pressed against a module while a tensile stress is applied when it is mounted as a diaphragm or the like in a device. preferable.
• the mass ratio (A/B) of the polyphenylene sulfide fiber (A) and the copolymerized polyphenylene sulfide fiber (B) is preferably 0.01 or more, and 0.1 or more. It is more preferably 0.5 or more. Also, it is preferably 50 or less, more preferably 25 or less, and even more preferably 2 or less.
• the air permeability of the polyphenylene sulfide fiber nonwoven fabric of the present invention is preferably 1 to 150 cc/cm 2 /s.
• the air permeability is preferably 1 cc/cm 2 /s or more, more preferably 3 cc/cm 2 /s or more, and even more preferably 5 cc/cm 2 /s or more, ions and the like when used in a diaphragm or the like can be reduced. Improves permeability.
• the air permeability is preferably 150 cc/cm 2 /s or less, more preferably 120 cc/cm 2 /s or less, still more preferably 100 cc/cm 2 /s or less, so that the nonwoven fabric has sufficient mechanical strength. As a result, breakage during the manufacturing process is less likely to occur, and process passability is improved. Also, when used for a diaphragm or the like, it is less likely to break or crack during assembly.
• the air permeability of the nonwoven fabric in the present invention refers to the value measured by the method described in Examples.
• the diaphragm of the present invention contains the polyphenylene sulfide fiber nonwoven fabric of the present invention described above.
• the diaphragm is not particularly limited, but it plays a role of ion permeation and gas separation in, for example, a hydrogen production device, a fuel cell, or the like. Since the polyphenylene sulfide fiber nonwoven fabric of the present invention is excellent in mechanical strength even though it is thin and has a low basis weight, it is excellent in ion permeation efficiency and becomes a diaphragm that is resistant to tearing during mounting and use.
• the diaphragm of the present invention there is a laminate of the polyphenylene sulfide fiber nonwoven fabric of the present invention and other materials such as a porous film. Since the polyphenylene sulfide fiber nonwoven fabric of the present invention contains the copolymerized polyphenylene sulfide fiber (B) with a low melting point, it has excellent heat-sealing properties with other materials, and there is little delamination and a decrease in ion transmission efficiency between layers. It becomes a high-performance diaphragm.
• a preferred example of the method for producing the polyphenylene sulfide fiber nonwoven fabric of the present invention and a diaphragm containing the same is as follows. First, the precursors of polyphenylene sulfide fiber (A), copolymerized polyphenylene sulfide fiber (B) and polyphenylene sulfide fused portion (C) are dispersed in water to prepare a papermaking stock solution, followed by papermaking and drying. Next, the precursor of the polyphenylene sulfide fused portion (C) is thermally fused between the fibers by a heat calender or the like to form the polyphenylene sulfide fused portion (C). In the present invention, the polyphenylene sulfide fused portion (C) can be formed by preferably using unstretched polyphenylene sulfide fibers as its precursor and fusing them by heat calendering or the like.
• the method for producing a polyphenylene sulfide fiber nonwoven fabric and a diaphragm using the polyphenylene sulfide fiber (A), the copolymerized polyphenylene sulfide fiber (B), and the unstretched polyphenylene sulfide fiber, which are preferably used in the present invention, will be described below using papermaking nonwoven fabric as an example. A specific description will be given.
• the polyphenylene sulfide to be used is preferably dried before being melt-spun for the purpose of preventing water contamination and removing oligomers, in order to improve spinnability.
• drying conditions vacuum drying at 100 to 200° C. for 1 to 24 hours is usually used.
• melt spinning a melt spinning method using an extruder such as a pressure melter type, single-screw or twin-screw extruder type can be applied.
• the extruded polyphenylene sulfide passes through a pipe, is weighed by a weighing device such as a gear pump, passes through a foreign matter-removing filter, and is led to a spinneret.
• the temperature from the polymer pipe to the spinneret is preferably 280° C. or higher to improve fluidity, and preferably 380° C. or lower to suppress thermal decomposition of the polymer.
• the polyphenylene sulfide fiber used in the present invention is a composite fiber
• the polyphenylene sulfide and the other component resin are melted separately, and weighed by a known weighing device such as a gear pump through a polymer pipe, and filtered to remove foreign matter. After passing through, each lead to a spinneret.
• a known weighing device such as a gear pump
• Each polymer led to the spinneret is shape-regulated into an arbitrary composite form in the spinneret, joined together, and discharged from the spinneret hole as a composite fiber.
• the spinneret used for ejection preferably has a spinneret hole diameter D of 0.1 mm or more and 0.6 mm or less. It is preferable that L/D defined as the quotient obtained by dividing the pore size D by the pore diameter D be 1 or more and 10 or less.
• the polyphenylene sulfide fibers discharged from the nozzle holes are cooled and solidified by blowing cooling air (air).
• the temperature of the cooling air can be determined in balance with the cooling air velocity from the viewpoint of cooling efficiency, and is preferably 30° C. or less. By setting the temperature of the cooling air to preferably 30° C. or less, the solidification behavior due to cooling is stabilized, and polyphenylene sulfide fibers with high fiber diameter uniformity can be obtained.
• the speed of the cooling air is preferably 10 m/min or more from the viewpoint of cooling efficiency and fineness uniformity, and preferably 100 m/min or less from the viewpoint of spinning stability.
• the unstretched fibers that have been cooled and solidified are taken up by rollers (godet rollers) that rotate at a constant speed.
• the take-up speed is preferably 300 m/min or more for improving linear uniformity and productivity, and preferably 2000 m/min or less for preventing yarn breakage.
• the undrawn fibers obtained in this way are subjected to a drawing process after being wound once or continuously after being taken off. Stretching is carried out by running the film over a heated first roller or a heating device provided between the first and second rollers, such as a heating bath or a hot plate.
• the drawing conditions are determined by the mechanical properties of the obtained undrawn fiber, but the drawing temperature is determined by the temperature of the heated first roller or the temperature of the heating device provided between the first roller and the second roller.
• the magnification is determined by the ratio of the peripheral speeds of the first roller and the second roller.
• the temperature of the heated first roller or heating device in the stretching step is preferably 80°C or higher and 130°C or lower.
• the temperature of the second roller is preferably the temperature of the heated first roller or the heating device +20° C. or less.
• the drawn fibers may be heated by a heated third roller or by a heating device provided between the second and third rollers for heat setting.
• the heat setting temperature for heat setting is preferably 180 to 240.degree.
• the shrinkage rate can be reduced by thermal crystallization.
• the heat setting temperature to 240° C. or lower, fusion of the fibers to the roller can be suppressed, and deterioration of the processability can be prevented.
• the adhesion rate of the papermaking dispersant is preferably 1 to 6% by mass relative to the mass of the fiber.
• the adhesion rate is preferably 1 to 6% by mass relative to the mass of the fiber.
• the obtained fibers may be crimped by a crimper and heat-set by a setter.
• the fibers are entangled with each other, so that the adhesion area between the fibers increases, and a nonwoven fabric having excellent mechanical strength can be obtained.
• the number of crimps in the above crimping is preferably 2 to 15 crimps/25 mm.
• the number of crimps is preferably 2 crimps/25 mm or more, the fibers are easily entangled with each other, resulting in a nonwoven fabric having excellent mechanical strength. Further, by setting the number of crimps to preferably 15 crimps/25 mm or less, the dispersibility of the fibers in the dispersion liquid is improved, resulting in a homogeneous nonwoven fabric.
• the heat setting temperature by the setter is preferably 80 to 100°C.
• the heat setting temperature by the setter is preferably 80 to 100°C.
• cut fibers can be obtained by cutting the obtained fibers to a predetermined length with a cutter.
• the fiber length of the cut fiber is preferably 0.5 to 15 mm.
• the heat setting temperature is preferably 210°C or less.
• the heat setting temperature is preferably 210° C. or lower, more preferably 190° C. or lower, and even more preferably 150° C. or lower.
• the cut fiber obtained above can be obtained in the same manner as the polyphenylene sulfide fiber (A).
• Cut fibers of undrawn fibers can be obtained in the same manner as in the production method of polyphenylene sulfide fibers (A), except that drawing and heat setting are not performed.
• the raw material polymers may be the same as long as they are within the range of components described above.
• Each of the three types of cut fibers obtained by the above method is dispersed in water. Furthermore, these dispersions are mixed in a desired ratio to obtain a papermaking dispersion.
• the melting point (Tm ⁇ L) in the present invention can be adjusted by the melting point of the copolymerized polyphenylene sulfide fiber (B) that constitutes the nonwoven fabric, and the melting point of the copolymerized polyphenylene sulfide fiber (B) is usually It can be lowered by increasing the ratio, and can be improved by decreasing the copolymerization rate.
• the total amount of the three types of cut fibers relative to the total mass of the papermaking dispersion is preferably 0.05 to 5% by mass.
• the total amount 0.05% by mass or more the production efficiency can be improved and the load of the dehydration process can be reduced.
• a dispersion state improves and a uniform wet-laid nonwoven fabric can be obtained.
• the dispersion liquid may be obtained by separately preparing dispersion liquids of three types of cut fibers in advance and then mixing them, or directly preparing a dispersion liquid containing three types of cut fibers.
• the method of preparing dispersions of each fiber separately and mixing them is preferable in that the stirring time can be controlled separately according to the shape and characteristics of each fiber.
• the method of adjusting the liquid is preferable in terms of process simplification.
• Dispersants and oil agents containing cationic, anionic, nonionic surfactants, etc. are used to improve the water dispersibility of the papermaking dispersion, A viscous agent to prevent this, and an antifoaming agent to suppress the generation of foam may be added.
• the dispersion for papermaking prepared as described above is made into paper using a paper machine such as a cylinder type, fourdrinier type, inclined net type, or a manual paper machine, and dried with a Yankee dryer, a rotary dryer, or the like. Web. After that, a heat and pressure treatment is applied to obtain a nonwoven fabric.
• a heat and pressure treatment is applied to obtain a nonwoven fabric.
• simultaneous application of heat and pressure is referred to as heating and pressure treatment, and is distinguished from treatment such as drying, which is performed only by heating without applying pressure.
• a dry web is a wet paper-made nonwoven fabric that has not been subjected to this heat and pressure treatment.
• the polyphenylene sulfide fused portion (C) is produced by subjecting the above-described unstretched polyphenylene sulfide fiber to heat and pressure treatment, etc., in terms of simplicity and low cost. is preferred. In this case, it is preferable to suppress crystallization during the manufacturing process of the dry web as much as possible.
• the drying temperature in the papermaking process is preferably 80 to 150°C, more preferably 90 to 140°C. It is also preferable to shorten the passage time of the drying process to suppress crystallization.
• the drying temperature in the papermaking process refers to the highest processing temperature (ambient temperature) during drying in the papermaking process.
• the nonwoven fabric of the present invention it is preferable to apply heat and pressure to a dry web made by blending three types of cut fibers.
• the unstretched polyphenylene sulfide fibers are melted and softened to form the polyphenylene sulfide fused portion (C).
• Any means may be used as the heating/pressurizing means, and for example, hot pressing with a flat plate or the like, hot calendering, or the like can be employed.
• a hot calender is preferable because it can be processed continuously.
• the hot calender rolls can be metal-metal rolls, metal-paper rolls, metal-rubber rolls, and the like.
• the temperature conditions for the heating and pressure treatment are preferably a temperature above the glass transition temperature of the unstretched polyphenylene sulfide fiber and a temperature below the melting point of the copolymerized polyphenylene sulfide fiber (B).
• the heating temperature By setting the heating temperature to preferably 150° C. or higher, the unstretched polyphenylene sulfide fibers are melted and softened to form polyphenylene sulfide fused portions (C), resulting in a nonwoven fabric having excellent mechanical properties.
• the heating temperature By setting the heating temperature to preferably 240° C.
• the copolymerized polyphenylene sulfide fiber (B) having a low melting point can be completely fused to prevent damage to the fiber shape.
• a pressure of 98 to 7000 N/cm is preferable when calendering is used as the heat/pressure treatment.
• the polyphenylene sulfide fused portion (C) can be formed, and the nonwoven fabric has excellent mechanical properties.
• the process speed is preferably 1 to 30 m/min. Good work efficiency can be obtained by setting the speed to preferably 1 m/min or more, more preferably 2 m/min.
• the speed can be conducted to the fibers inside the nonwoven fabric, and effective heat fusion of the fibers can be obtained.
• the diaphragm of the present invention can use the polyphenylene sulfide fiber nonwoven fabric of the present invention as it is, but can also be manufactured by laminating other materials such as porous films as necessary. In the case of lamination, it is preferable to heat-seal them by thermal calendering or the like. As for the heating temperature during heat calendering, by setting the heating temperature to 220° C. or less, the fiber morphology of the polyphenylene sulfide fibers (A) and the copolymerized polyphenylene sulfide fibers (B) in the polyphenylene sulfide fiber nonwoven fabric of the present invention is not impaired. , it becomes a diaphragm having both high tear strength and tensile strength.
• the mol % of the repeating unit of the polyphenylene sulfide fused portion (C) is 810 cm from the infrared absorption spectrum in the region composed of polyphenylene sulfide obtained at a magnification of 150 times as described above, in the portion that has lost its fiber shape and has become a film. It was calculated from the peak intensity derived from the C—H out-of-plane deformation angle of the benzene para-substituted product near ⁇ 1 using a calibration curve obtained from each peak intensity of a standard sample of known mol %.
• melt point (Tm-L) of polyphenylene sulfide fiber nonwoven fabric The melting point of the polyphenylene sulfide fiber nonwoven fabric is obtained by heating the nonwoven fabric from 50 ° C. to 320 ° C. at a rate of 16 ° C./min with DSC (“Q1000” manufactured by TA Instruments Inc.), and the obtained DSC curve shows a temperature of 200 ° C. or higher.
• DSC melting point
• Metsuke According to JISL1913 (2010) mass per unit area, collect 3 pieces of 10 cm ⁇ 10 cm sample pieces, weigh each mass (g) in the standard state, and the average value is the mass per 1 m 2 (g / m 2 ).
• Thickness JISP8118 (2014) Thickness: Twenty 10 cm x 10 cm sample pieces were collected according to A method, and the thickness of each of the 20 test pieces was measured using a micrometer (manufactured by Mitutoyo Co., Ltd.). The arithmetic average value was taken as the thickness ( ⁇ m) of the nonwoven fabric.
• Tear strength JISL1096 (2010) tear strength: According to the D method (pendulum method), a test piece of 63 mm ⁇ 100 mm is measured vertically (direction of progress in the nonwoven fabric manufacturing process) and horizontally (width direction in the nonwoven fabric manufacturing process). Directions were measured. Using an Elmendorf type tear tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), a 20 mm cut is made at right angles in the center of both grips of the test piece, and the remaining 43 mm is torn in the vertical and horizontal directions to measure the strength exhibited. did. The tear strength (N) of the nonwoven fabric was obtained by measuring five times in each of the vertical and horizontal directions for each level, and calculating the arithmetic average value.
• Tensile strength According to JISL1913 (2010) Tensile strength and elongation (standard time), the tensile strength is measured in each direction of the nonwoven fabric, vertical (progressing direction of nonwoven fabric manufacturing process) and horizontal (width direction of nonwoven fabric manufacturing process). rice field. Using Tensilon (“UTM-III-100” manufactured by Orientec Co., Ltd.), the maximum point load was measured under the conditions of a sample width of 15 mm, an initial length of 20 mm, and a tensile speed of 20 mm/min. Each level was measured five times in each of the vertical and horizontal directions, and the arithmetic average value was determined as the tensile strength (N/15 mm) of the nonwoven fabric.
• Breathability JISL1913 (2010) Breathability: Three 15 cm x 15 cm specimens were collected according to the Frazier method, and a permeability tester ("FX3300" manufactured by TEXTTEST AG) was used to test specimen 3 at a test pressure of 125 Pa. The air permeability of the sheet was measured, and the arithmetic average value was defined as air permeability (cm 3 /cm 2 /s).
• a pixel-by-pixel infrared absorption spectrum measurement was performed on the processed image, and the peak intensity derived from the benzene para-substituted CH out-of-plane bending vibration appearing around 810 cm ⁇ 1 revealed the polyphenylene sulfide fiber (A ) and copolymerized polyphenylene sulfide fibers (B) were distinguished and their existence was confirmed.
• the mol % of the repeating units of the polyphenylene sulfide fiber (A) and the copolymerized polyphenylene sulfide fiber (B) is the benzene para-substituted product near 810 cm -1 from the infrared absorption spectrum in each region obtained at 150 times magnification as described above.
• polyphenylene sulfide was discharged from a nozzle having 36 holes with a hole diameter D of 0.23 mm and a land length L of 0.3 mm under the conditions of a single hole discharge rate of 0.5 g/min.
• a spinneret was used in which the introduction hole positioned directly above the spinneret hole was a straight hole, and the connecting portion between the introduction hole and the spinneret hole was tapered.
• the polyphenylene sulfide extruded from the die was passed through a 50-mm heat-retaining area, and then air-cooled over a length of 1.0 m using a uniflow cooling device at a temperature of 25° C. and a wind speed of 18 m/min. After that, an oil solution was applied, and the 36 filaments were wound by a winder through the first godet roller and the second godet roller of 1000 m/min together to obtain an unstretched fiber.
• the obtained unstretched fiber is taken up by a feed roller attached to a nip roller, and after applying tension to the unstretched fiber with the first roller, the first roller and the first roller heated to 90 ° C. and 100 ° C. respectively.
• Heat drawing was carried out by making 2 rollers rotate 6 times. Furthermore, the third roller heated to 230° C. was rotated 6 times for heat setting. The draw ratio was 3.85 times, and after the third roller, the fiber was drawn by a non-heated roller with a peripheral speed of 400 m/min, and then 2% by mass of a dispersant was applied to the fiber mass using guide oil supply. .
• the draw ratio was 3.85 times, and after the third roller, the fiber was drawn by a non-heated roller with a peripheral speed of 400 m/min, and then 2% by mass of a dispersant was applied to the fiber mass using guide oil supply. . Subsequently, after applying crimps of 8 crests/25 mm with a crimper, heat setting was performed at 70° C. for 1 minute with a setter. After that, by cutting the obtained fibers with a cutter, cut fibers having an average fiber length of 6 mm were obtained.
• the m-phenylene sulfide unit of the polyphenylene sulfide fiber (B) thus obtained was 10.0% by mol % measured by a microscopic infrared spectrophotometer.
• the p-phenylene sulfide unit of the unstretched polyphenylene sulfide fiber thus obtained was 96.0% by mol % measured by a micro-infrared spectrophotometer.
• Example 1 40% by mass of cut fiber of polyphenylene sulfide fiber (A) obtained in Reference Example 1, 40% by mass of cut fiber of copolymerized polyphenylene sulfide fiber (B) having a copolymerization molar ratio of 10 mol% obtained in Reference Example 2, Reference Example 20% by mass of cut fibers of the unstretched polyphenylene sulfide fibers obtained in 3 were dispersed in water to prepare a dispersion having a fiber concentration of 0.07% by mass. This dispersion was used to prepare a wet paper on a manual paper machine. The web obtained by dewatering with a roller is dried at 110 ° C.
• Examples 2 to 7 A nonwoven fabric was obtained in the same manner as in Example 1, except that the mass ratio of polyphenylene sulfide fiber (A), copolymerized polyphenylene sulfide fiber (B), and unstretched polyphenylene sulfide fiber was changed. Table 1 shows the evaluation results of the nonwoven fabric.
• Example 1 Partially dried in the drying step in the same manner as in Example 1 except that 50% by mass of polyphenylene sulfide fiber (A) and 50% by mass of copolymerized polyphenylene sulfide fiber (B) were used instead of using unstretched polyphenylene sulfide fiber. A non-woven fabric was obtained even though breakage occurred at the end. Table 2 shows the evaluation results of the nonwoven fabric.
• Example 2 A nonwoven fabric was obtained in the same manner as in Example 1, except that 50% by mass of polyphenylene sulfide fiber (A) and 50% by mass of unstretched polyphenylene sulfide fiber were used instead of using copolymerized polyphenylene sulfide fiber (B). Table 2 shows the evaluation results of the nonwoven fabric.
• Example 3 A non-woven fabric was obtained in the same manner as in Example 1 except that the polyphenylene sulfide fiber (A) was not used and the copolymerized polyphenylene sulfide fiber (B) was 50% by mass and the unstretched polyphenylene sulfide fiber was 50% by mass. Table 2 shows the evaluation results of the nonwoven fabric.
• Example 4 A nonwoven fabric was obtained in the same manner as in Example 1, except that only unstretched polyphenylene sulfide fibers were used. Table 2 shows the evaluation results of the nonwoven fabric.
• Example 8-9 Comparative Examples 5-6
• a nonwoven fabric was obtained in the same manner as in Example 1, except that the melting point was changed by changing the copolymerization mol % of the copolymerized polyphenylene sulfide fiber (B).
• Table 3 shows the evaluation results of the nonwoven fabric.
• Example 10 A non-woven fabric was obtained in the same manner as in Example 1, except that the unstretched polyphenylene sulfide fiber was changed to the unstretched polyphenylene sulfide fiber obtained in Reference Example 4 with a low mol % of p-phenylene sulfide units. Table 3 shows the evaluation results of the nonwoven fabric.
• Example 7 A non-woven fabric was obtained in the same manner as in Example 1, except that the unstretched copolymerized polyphenylene sulfide fiber obtained in Reference Example 5 was used instead of the unstretched polyphenylene sulfide fiber. Table 3 shows the evaluation results of the nonwoven fabric.
• the polyphenylene sulfide fiber nonwoven fabrics obtained in Examples 1 to 10 contain polyphenylene sulfide fibers (A) and copolymerized polyphenylene sulfide fibers (B), have polyphenylene sulfide fused portions (C), and have high tear resistance. A nonwoven fabric with high tenacity and tensile strength was obtained.
• the polyphenylene sulfide fiber nonwoven fabric obtained in Comparative Example 1 did not have the polyphenylene sulfide fused portion (C) and had high tear strength, but a nonwoven fabric with sufficient tensile strength could not be obtained.
• the polyphenylene sulfide fiber non-woven fabric obtained in Comparative Example 2 did not contain the copolymerized polyphenylene sulfide fiber (B) and exhibited high tensile strength, but a non-woven fabric with sufficient tear strength could not be obtained.
• the polyphenylene sulfide fiber nonwoven fabric obtained in Comparative Example 3 did not contain the polyphenylene sulfide fiber (A) and had high tear strength, but a nonwoven fabric with sufficient tensile strength could not be obtained.
• the polyphenylene sulfide fiber nonwoven fabric obtained in Comparative Example 4 did not contain polyphenylene sulfide fiber (A) and copolymerized polyphenylene sulfide fiber (B), and the resulting nonwoven fabric had insufficient tear strength. In addition, the tensile strength was lower than that of Comparative Example 2, which had similarly low tear strength.
• the polyphenylene sulfide fiber nonwoven fabric obtained in Comparative Example 5 has a low copolymerization molar ratio and contains a high melting point copolymerized polyphenylene sulfide fiber (B), and has a high melting point (Tm ⁇ L) and high tensile strength. However, a nonwoven fabric having sufficient tear strength could not be obtained.
• the polyphenylene sulfide fiber non-woven fabric obtained in Comparative Example 6 has a high copolymerization molar ratio and contains a low melting point copolymerized polyphenylene sulfide fiber (B), and has a low melting point (Tm-L). Although the nonwoven fabric exhibited high tensile strength, a nonwoven fabric with sufficient tear strength could not be obtained.
• the polyphenylene sulfide fiber nonwoven fabric obtained in Comparative Example 7 does not have unstretched polyphenylene sulfide fibers forming the polyphenylene sulfide fused portion (C) and has high tear strength, but the nonwoven fabric has sufficient tensile strength. could not get

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