WO2023136141A1 - 耐炎化ポリフェニレンエーテル繊維及び補強繊維を含む耐炎化不織布、耐炎化ポリフェニレンエーテル及び補強繊維を含む耐炎化成型体、並びにそれらの製造方法 - Google Patents

耐炎化ポリフェニレンエーテル繊維及び補強繊維を含む耐炎化不織布、耐炎化ポリフェニレンエーテル及び補強繊維を含む耐炎化成型体、並びにそれらの製造方法 Download PDF

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WO2023136141A1
WO2023136141A1 PCT/JP2022/048253 JP2022048253W WO2023136141A1 WO 2023136141 A1 WO2023136141 A1 WO 2023136141A1 JP 2022048253 W JP2022048253 W JP 2022048253W WO 2023136141 A1 WO2023136141 A1 WO 2023136141A1
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Prior art keywords
flame
resistant
polyphenylene ether
nonwoven fabric
fibers
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PCT/JP2022/048253
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English (en)
French (fr)
Japanese (ja)
Inventor
章文 安井
健太 北條
智佳子 西光
輝之 谷中
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東洋紡エムシー株式会社
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Priority to JP2023573973A priority Critical patent/JPWO2023136141A1/ja
Publication of WO2023136141A1 publication Critical patent/WO2023136141A1/ja

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—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

Definitions

  • the present invention relates to a flame-resistant nonwoven fabric containing flame-resistant polyphenylene ether fibers and reinforcing fibers, a flame-resistant molded article containing flame-resistant polyphenylene ether and reinforcing fibers, and methods for producing them.
  • Polyphenylene ether (hereinafter also referred to as PPE) is excellent in heat resistance, flame retardancy, strength, chemical resistance, etc., so molded articles formed from polyphenylene ether are used in a wide range of fields.
  • Flame-resistant polyphenylene ether fibers, which are flame-resistant materials, and nonwoven fabrics made of such fibers have been known (for example, Patent Document 1). Such molded bodies were not known.
  • fiber-reinforced resin composites made of thermoplastic resin and reinforcing fibers such as carbon fiber and glass fiber are lightweight and have excellent specific strength and specific rigidity. It is used in a wide range of applications such as automobile applications and aircraft applications.
  • reinforcing fibers are sometimes used as continuous fibers in order to improve mechanical properties.
  • continuous fibers have poor formability, and it may be difficult to produce a fiber-reinforced resin composite having a complicated shape. Therefore, it is known to manufacture a fiber-reinforced resin composite having a complicated shape by using discontinuous fibers as reinforcing fibers.
  • thermoplastic resin and carbon fiber and non-woven fabrics for forming the molded article
  • molding materials for forming the molded article
  • a molded article made of a thermoplastic resin and carbon fibers in a specific weight ratio, wherein the carbon fibers are monofilament-like and have a specific weight average fiber length and orientation parameter, and a molding material therefor e.g. , U.S. Pat. No. 5,300,000, at least one first fiber as a fusion fiber made of a high-performance thermoplastic and at least one second fiber made of a high-performance material with a higher temperature stability compared to said fusion fiber.
  • Patent Document 5 A certain prepreg sheet (for example, Patent Document 5), a nonwoven fabric used for producing a heat-resistant resin composite containing heat-resistant thermoplastic fibers, reinforcing fibers, and polyester binder fibers (for example, Patent Document 6), etc. are known. ing.
  • Patent Document 1 discloses a non-woven fabric made of flame-resistant polyphenylene ether fiber, but the non-woven fabric is a non-woven fabric made only of flame-resistant polyphenylene ether fiber. No nonwoven fabric made of fibers was disclosed.
  • the nonwoven fabric of Patent Document 1 has a limiting oxygen index (LOI value) exceeding 40 and has high flame retardancy. However, it has limitations and is not sufficient in fields requiring even higher flame retardancy (for example, fields requiring flame retardancy with an LOI value of 50 or more).
  • Patent Documents 2 to 6 flame resistance was not considered, and it was not sufficient in the field of high flame retardancy.
  • an object of the present invention is to provide a flame-retardant nonwoven fabric containing a flame-resistant polyphenylene ether fiber and a reinforcing fiber imparted with higher flame retardancy (flame resistance) and heat resistance, and a flame-retardant fabric containing a flame-resistant polyphenylene ether and a reinforcing fiber.
  • An object of the present invention is to provide molded articles and methods for producing them.
  • the present inventors have found that a nonwoven fabric containing a flame-resistant polyphenylene ether fiber and a reinforcing fiber having a specific chemical structure detectable by infrared spectroscopy, a flame-resistant nonwoven fabric containing a flame-resistant polyphenylene ether and a reinforcing fiber
  • the present inventors have found that the above problems can be solved by using a molded product, and have completed the present invention. That is, the present invention consists of the following configurations.
  • the 1% mass loss temperature of the reinforcing fibers is preferably 400°C or higher.
  • the LOI value of the flame-resistant nonwoven fabric is preferably 50 or more.
  • the average fiber length of the reinforcing fibers is preferably 15 mm or more.
  • the thickness of the flame-resistant nonwoven fabric is preferably 1 mm or more and 30 mm or less.
  • the number of crimps in the flame-resistant polyphenylene ether fiber is preferably 2/25 mm or more and 24/25 mm or less.
  • the reinforcing fibers are preferably carbon fibers and/or glass fibers.
  • the present invention also provides a method for producing a flame-resistant nonwoven fabric containing flame-resistant polyphenylene ether fibers and reinforcing fibers, forming a nonwoven comprising polyphenylene ether fibers and reinforcing fibers; A step of heat-treating the obtained nonwoven fabric in air at 120° C. or higher and 240° C. or lower for 1 hour or longer and 30 hours or shorter to make it infusible; A method for producing a flame-resistant nonwoven fabric, comprising a step of heat-treating an infusibilized non-woven fabric in air at 260° C. or higher and 400° C. or lower for 0.1 hour or longer and 10 hours or shorter to make it flame resistant.
  • the LOI value of the flame-resistant molded body is preferably 46 or more.
  • the average fiber length of the reinforcing fibers is preferably 15 mm or more.
  • the reinforcing fibers are preferably carbon fibers and/or glass fibers.
  • the molded body is a molded body formed by pressing a nonwoven fabric containing polyphenylene ether fibers and reinforcing fibers and subjected to a flameproofing treatment.
  • the present invention provides a method for producing a flame-resistant molded article comprising flame-resistant polyphenylene ether and reinforcing fibers, comprising: pressing a nonwoven fabric containing polyphenylene ether fibers and reinforcing fibers to form a molded body; A step of heat-treating the obtained molded body in the air at 120° C. or more and 240° C. or less for 1 hour or more and 30 hours or less to make it infusible; It relates to a method for producing a flame-resistant molded article, comprising a step of heat-treating an infusibilized molded article in air at 260° C. or higher and 400° C. or lower for 0.1 hour or longer and 10 hours or shorter to make it flame resistant. .
  • A/B absorbance height ratio
  • the flame-resistant nonwoven fabric of the present invention is made of flame-resistant polyphenylene ether fibers and reinforcing fibers, so that the entanglement of the fibers can be controlled, and as a result, appropriate voids can be formed in the nonwoven fabric. It is considered that high flame retardancy is imparted. Therefore, the flame-resistant nonwoven fabric of the present invention can be suitably used for flame-resistant sheets and the like that require high flame retardancy.
  • a two-stage heat treatment infusibilization treatment and flameproofing treatment
  • the flame-resistant molded body of the present invention was measured by infrared spectroscopy, and the absorbance height A at the wavenumber 1732 cm
  • the absorbance height A at the wavenumber 1732 cm
  • A/B absorbance height ratio
  • the absorbance height B at a wavelength of 1600 cm ⁇ 1 from which it is derived
  • very high flame retardancy and heat resistance It shows the sex.
  • flame retardancy flame retardancy exceeding the flame retardancy expected from the flame retardancy of the flame-resistant polyphenylene ether itself and the flame retardancy of the reinforcing fiber itself is imparted.
  • the flame-resistant molded article of the present invention can be suitably used for flame-resistant parts and the like that require high flame retardancy.
  • a two-step heat treatment infusibilization treatment and flameproofing treatment is performed to produce a flameproof molded product having extremely high flame retardancy, flame resistance, heat resistance, etc. It is something that can be done.
  • the flame-resistant nonwoven fabric of the present invention contains a flame-resistant polyphenylene ether fiber and a reinforcing fiber, and the flame-resistant polyphenylene ether fiber is measured by infrared spectroscopy, and the wavenumber derived from C ⁇ O stretching vibration is 1732 cm ⁇ 1 .
  • the absorbance height ratio (A/B) between the absorbance height A of the benzene ring and the absorbance height B at a wavelength of 1600 cm derived from skeletal vibration due to stretching between the carbons of the benzene ring is 0.42 or more. Characterized by
  • the LOI value of the flame-resistant nonwoven fabric of the present invention is preferably 50 or more, more preferably 60 or more, and even more preferably 65 or more. It is preferable that the LOI value is within the above range because the obtained flame-resistant nonwoven fabric has excellent flame retardancy.
  • the LOI value is the limiting oxygen index, and the larger the LOI value, the more excellent the flame retardancy. Therefore, the larger the LOI value, the better, and the upper limit is not particularly limited.
  • the basis weight of the flame-resistant nonwoven fabric of the present invention is not particularly limited, and can be appropriately determined according to the purpose for which the nonwoven fabric is used. is more preferred. Also, it is preferably 3000 g/m 2 or less, more preferably 2000 g/m 2 or less.
  • the thickness of the flame-resistant nonwoven fabric of the present invention is not particularly limited, and can be appropriately determined according to the purpose for which the nonwoven fabric is used. is more preferable, and it is even more preferable to be about 1 mm or more. Also, the thickness is preferably about 100 mm or less, more preferably about 80 mm or less, and even more preferably about 30 mm or less.
  • the mass ratio of the flame-resistant polyphenylene ether fiber and the reinforcing fiber contained in the flame-resistant nonwoven fabric of the present invention is not particularly limited, and can be appropriately determined according to the purpose for which the nonwoven fabric is used.
  • the fiber mass ratio is preferably about 95/5 or more and 5/95 or less, more preferably about 90/10 or more and 10/90 or less, and about 60/40 or more and 40/60 or less. is more preferred. It is preferable that the mass ratio is in the above range because a uniform nonwoven fabric with good handleability can be obtained.
  • the content of the flame-resistant polyphenylene ether in the flame-resistant nonwoven fabric of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the flame-resistant nonwoven fabric. Also, the content is preferably 95% by mass or less, more preferably 90% by mass or less, relative to the total amount of the flame-resistant nonwoven fabric. When the content of the flame-resistant polyphenylene ether is within the above range, both flame retardancy and strength can be achieved, which is preferable.
  • the method for producing the flame-resistant nonwoven fabric of the present invention is not particularly limited, it can be suitably produced by the method for producing the flame-resistant nonwoven fabric of the present invention, which will be described later.
  • the flame-resistant polyphenylene ether fibers, reinforcing fibers, etc. contained in the flame-resistant nonwoven fabric of the present invention will be described in detail below.
  • the flameproof polyphenylene ether fiber used in the present invention is formed by subjecting polyphenylene ether fiber to a flameproof treatment.
  • the flame-resistant treatment may be performed on the polyphenylene ether fiber before forming the non-woven fabric, or may be performed on the non-woven fabric formed from the untreated polyphenylene ether fiber and the reinforcing fiber, but the flame-resistant non-woven fabric can be produced more easily. More preferred is the method of flameproofing the nonwoven fabric.
  • the absorbance height ratio (A/B) to the absorbance height B at the derived wavelength of 1600 cm ⁇ 1 is 0.42 or more.
  • the peak at a wavelength of 1732 cm ⁇ 1 derived from the C ⁇ O stretching vibration is formed by flameproofing the polyphenylene ether fiber.
  • the absorbance height ratio is within the above range, extremely high flame retardancy can be imparted.
  • the LOI value (limiting oxygen index) of the flame-resistant polyphenylene ether fiber itself exceeds 30. It is possible. Also, heat resistance and the like can be imparted.
  • the flame-resistant nonwoven fabric of the present invention contains such flame-resistant polyphenylene ether fibers and reinforcing fibers, so that extremely high flame retardancy (flame resistance) and heat resistance can be imparted.
  • the upper limit of the absorbance height ratio is not particularly limited, but is preferably 3.0 or less, more preferably 2.0 or less, and further preferably 1.5 or less. preferable. The flameproof treatment method will be described later.
  • the number of crimps of the flame-resistant polyphenylene ether fiber used in the present invention is preferably 2/25 mm or more and 24/25 mm or less. By setting the number of crimps within the above range, the entanglement between the flame-resistant polyphenylene ether fiber and the reinforcing fiber is improved, and a highly uniform nonwoven fabric can be formed, which is preferable. Since the number of crimps of the flame-resistant polyphenylene ether fiber is the same as the number of crimps of the polyphenylene ether fiber before the flame-retarding treatment, the preferable range of the number of crimps and the crimping method are those described in the later-described polyphenylene ether fiber. is the same as
  • the polyphenylene ether fiber to be flameproofed is not particularly limited as long as it contains a polyphenylene ether component.
  • the polyphenylene ether component is not particularly limited, and those commonly used in this field can be mentioned.
  • the following general formula (1) (wherein R 1 and R 2 are each independently a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and R 3 is each independently represents a hydrocarbon group having 1 or more and 10 or less carbon atoms which may have a substituent)
  • R 1 and R 2 in the general formula (1) include hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, and cyclopentyl.
  • alkyl groups having 1 to 10 carbon atoms such as hexyl group, cyclohexyl group, octyl group and decyl group;
  • Aralkyl groups having 7 to 10 carbon atoms such as the following aryl group, benzyl group, 2-phenylethyl group and 1-phenylethyl group can also be mentioned.
  • the substituent includes a halogen atom such as a fluorine atom, an alkoxy group such as a methoxy group, and the like.
  • a halogen atom such as a fluorine atom
  • an alkoxy group such as a methoxy group
  • Specific examples of the hydrocarbon group having a substituent include, for example, a trifluoromethyl group.
  • R 1 and R 2 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • R 3 in the general formula (1) examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl.
  • alkyl groups having 1 to 10 carbon atoms such as octyl and decyl groups
  • aryl groups having 6 to 10 carbon atoms such as phenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl groups
  • aralkyl groups having 7 or more and 10 or less carbon atoms such as groups, 2-phenylethyl groups, 1-phenylethyl groups, and the like.
  • examples of the substituent include a halogen atom such as a fluorine atom and an alkoxy group such as a methoxy group.
  • Specific examples of the hydrocarbon group having a substituent include, for example, a trifluoromethyl group.
  • R 3 is preferably a methyl group.
  • repeating unit of general formula (1) examples include 2,6-dimethyl-1,4-phenylene ether, 2,6-diethyl-1,4-phenylene ether, 2-methyl-6-ethyl Repeating units derived from -1,4-phenylene ether, 2,6-dipropyl-1,4-phenylene ether can be mentioned. Among these, repeating units derived from 2,6-dimethyl-1,4-phenylene ether are preferred.
  • the polyphenylene ether can contain a repeating unit other than the general formula (1) within a range that does not impair the effects of the present invention.
  • the content of repeating units other than those of general formula (1) is not particularly limited as long as it does not impair the effects of the present invention. Preferably, it is more preferably not included.
  • the weight average molecular weight (Mw) is preferably 40,000 or more, more preferably 50,000 or more. Also, the weight average molecular weight (Mw) is preferably 100,000 or less, more preferably 80,000 or less. Also, the number average molecular weight (Mn) is preferably 7,000 or more, more preferably 8,000 or more. Also, the number average molecular weight (Mn) is preferably 30,000 or less, more preferably 20,000 or less. Also, the molecular weight distribution (Mw/Mn) is preferably 3.5 or more and 8.0 or less, more preferably 4.0 or more and 6.0 or less.
  • Polyphenylene ether generally has a high melt viscosity, and when polyphenylene ether is contained in a high content, it was considered difficult to melt mold it alone. Therefore, when obtaining a polyphenylene ether melt-spun fiber, a method using a polyphenylene ether containing a polyphenylene ether component having a rearrangement structure, a polyphenylene ether component having a high glass transition temperature and a polyphenylene ether component having a low glass transition temperature It is preferable to use a method of mixing By these methods, the melt viscosity of the polyphenylene ether can be lowered, so that the polyphenylene ether can be melted and a melt-spun fiber can be formed.
  • polyphenylene ether having rearrangement structure examples include the following general formula (2): (wherein R 1 and R 2 are each independently a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and R 3 is each independently A hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R 3′ represents a divalent group in which one hydrogen atom is removed from R 3 ) It is preferable to use a polyphenylene ether containing a polyphenylene ether component having a rearranged structure represented by. By having such a dislocation structure, the fluidity is improved to the extent that melt molding is possible, and melt-spun fibers, non-woven fabrics, and the like can be formed.
  • R 1 , R 2 , and R 3 in general formula (2) are the same as those in general formula (1).
  • " ⁇ " in the general formula (2) indicates that the structure beyond it is not particularly limited.
  • the "-" portion may be formed from phenylene ether units that are continuous with para bonds, and may have a portion that is partially ortho-bonded therein.
  • R 3′ represents a divalent group obtained by removing one hydrogen atom from R 3 and is preferably a methylene group.
  • the polyphenylene ether component having a rearrangement structure is a homopolymer having a repeating unit of the general formula (1), a copolymer containing two or more different repeating units of the general formula (1), or the general formula
  • a copolymer containing repeating units of formula (1) and repeating units other than formula (1) preferably has a dislocation structure represented by formula (2).
  • the amount of rearrangement in the polyphenylene ether component having the rearrangement structure is not particularly limited, but is preferably 0.01 mol% or more with respect to all polyphenylene ether structural units in the polyphenylene ether component. It is more preferably 0.05 mol % or more, still more preferably 0.1 mol % or more, and particularly preferably 0.15 mol % or more. Further, it is preferably 2 mol % or more in order to obtain fine fibers with a single filament fineness of 15 dtex or less.
  • the upper limit of the dislocation amount is not particularly limited, but is preferably 20 mol% or less, more preferably 18 mol% or less, further preferably 5 mol% or less, and 4 mol% or less.
  • the amount of rearrangement in the polyphenylene ether component having a rearrangement structure is within the above range, the fluidity is improved to the extent that melt molding is possible, and a melt-spun fiber can be obtained, which is preferable.
  • the dislocation amount can be measured by the method described in Examples.
  • the method for forming the polyphenylene ether component having the rearrangement structure is as described below.
  • the method for lowering the melt viscosity by mixing polyphenylene ethers having a high Tg and a low Tg will be described in the method for producing polyphenylene ether fibers.
  • the polyphenylene ether fiber used in the present invention can contain a resin component other than the polyphenylene ether component.
  • Resin components other than polyphenylene ether include styrene, polyethylene, polypropylene, polyamides such as polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 66, polyamide 6T and polyamide 6T/11, and polyesters such as polyethylene terephthalate and polybutylene terephthalate. , polycarbonate, and the like.
  • the content is preferably 5% by mass or less, more preferably 2% by mass or less, and more preferably not contained (0% by mass).
  • the content of polyphenylene ether is preferably 95% by mass or more, more preferably 98% by mass or more, in all components forming the fiber, and substantially only polyphenylene ether (100% by mass) is more preferable.
  • the content of the polyphenylene ether in the polyphenylene ether fiber is within the above range, the obtained fiber not only has excellent mechanical strength, but also has excellent heat resistance, chemical resistance, flame retardancy, etc., which is preferable. .
  • Additives such as lubricants, plasticizers, antioxidants, UV absorbers, dulling agents, and antistatic agents can also be added to the polyphenylene ether fiber within a range that does not impair the effects of the present invention.
  • Polyphenylene ether fibers can be produced by various production methods such as melt spinning, dry spinning, and wet spinning. Among these, melt spinning is preferable because productivity can be increased.
  • Polyphenylene ether which is a raw material, is put into an extruder 2 equipped with a cylinder and a screw from a hopper 1 in FIG. It can pass through and be discharged from the spinning nozzle 5 to obtain a melt-spun fiber.
  • a filter 6 made of metal nonwoven fabric or the like on the filter medium 4 . It is preferable to install the filter 6 because it is possible to remove foreign substances and to prevent clogging of the filter medium 4 and the like.
  • a heat insulating space 7 is provided immediately below the spinning nozzle 5, and an inert gas such as nitrogen is introduced 8 into the area for spinning. More preferably, the torch 9 introduces heated inert gas.
  • the temperature of the heated inert gas is preferably 100° C. or higher and 500° C. or lower, more preferably 200° C. or higher and 400° C. or lower.
  • the spinning speed is not particularly limited, and can be appropriately set according to the required fineness, etc., but in order to stably obtain fine fineness fibers, the spinning speed is about 100 m/min or more and 5000 m/min or less. 100 m/min or more and 3000 m/min or less is more preferable.
  • the single hole discharge rate of the spinning nozzle is preferably 1.0 g/min or less, more preferably 0.8 g/min or less, and even more preferably 0.6 g/min or less.
  • the lower limit of the single hole discharge rate is not particularly limited, but it is preferably 0.05 g/min or more, more preferably 0.1 g/min or more, and further preferably 0.12 g/min or more. preferable.
  • a homopolymer having a repeating unit of the general formula (1) or a copolymer containing two or more different repeating units of the general formula (1), or the general formula (1 ) and a copolymer having a repeating unit other than the repeating unit of general formula (1).
  • Examples of the content of repeating units other than those represented by general formula (1) in the copolymer include those described above. Among these, homopolymers having repeating units of the general formula (1) are preferred.
  • homopolymers having repeating units of the general formula (1) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4- phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether) and the like. (2,6-dimethyl-1,4-phenylene ether) is preferred.
  • poly(2,6-dimethyl-1,4-phenylene ether) commercially available products can be suitably used. Specifically, for example, PPO640, PPO646, PPOSA120 manufactured by SABIC Innovative Plastic, ) manufactured by Zylon S201A and Zylon S202A.
  • polyphenylene ether having a high Tg and a low Tg can be mixed to lower the melt viscosity.
  • the glass transition temperature of the polyphenylene ether component having a high glass transition temperature is preferably 170°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher.
  • the upper limit of the glass transition temperature is not particularly limited, it is preferably 230° C. or less. It is preferable that the raw material polyphenylene ether have a glass transition temperature within the above range, since a polyphenylene ether fiber having high heat resistance can be obtained.
  • the glass transition temperature of the polyphenylene ether component having a low glass transition temperature is preferably less than 170°C.
  • the content of the polyphenylene ether having a glass transition temperature of 170° C. or higher is preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass, in the raw polyphenylene ether component. It is more preferable that it is above.
  • the upper limit of the content of the polyphenylene ether having a glass transition temperature of 170° C. or higher is not particularly limited, but is preferably 100% by mass or less. In the present invention, if the polyphenylene ether having a high glass transition temperature (that is, a high molecular weight) is included in the above range, the obtained polyphenylene ether fiber is excellent in mechanical strength, heat resistance, chemical resistance, flame retardancy, etc. Therefore, it is preferable.
  • resin components and additives other than the polyphenylene ether component can be included along with the raw material polyphenylene ether. Resin components and additives other than the polyphenylene ether component are as described above. In addition, the content of resin components other than the polyphenylene ether component is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably not contained (0% by mass).
  • a single-screw extruder or a twin-screw extruder that can be commonly used in this field can be used.
  • the peripheral speed of the screw is not particularly limited, and can be within the range normally used in this field. However, when forming fibers using polyphenylene ether having a rearranged structure, the peripheral speed of the screw is required to cause a rearrangement reaction of the polyphenylene ether as a raw material, and is 3.6 m / min or more. It is preferably 3.7 m/min or more, more preferably 3.8 m/min or more.
  • the upper limit of the peripheral speed of the screw is not particularly limited, but is preferably 94.2 m/min or less.
  • the screw rotation speed and setting the peripheral speed of the screw by increasing the screw rotation speed and setting the peripheral speed of the screw to 3.6 m / min or more, a high shearing force can be applied to the raw material polyphenylene ether in the cylinder, and as a result, the polyphenylene ether molecules It is capable of chain scission to form a polyphenylene ether having a rearranged structure. Formation of the polyphenylene ether having the rearrangement structure enables melt spinning of the polyphenylene ether.
  • the temperature in the cylinder is, for example, preferably 250° C. or higher and 350° C. or lower, more preferably 280° C. or higher and 330° C. or lower.
  • polyphenylene ether fibers used in the present invention may be short fibers, and can be obtained, for example, by cutting the tow-shaped fibers obtained by combining the polyphenylene ether fibers.
  • the glass transition temperature of the polyphenylene ether fiber used in the present invention is preferably 170°C or higher, more preferably 175°C or higher, and even more preferably 180°C or higher. Since the glass transition temperature is within the above range, extremely high heat resistance can be imparted.
  • the upper limit is not particularly limited, it is preferably 300° C. or lower, more preferably 250° C. or lower.
  • the polyphenylene ether fibers used in the present invention are preferably crimped because they are well entwined with the reinforcing fibers and can form a highly uniform nonwoven fabric.
  • the number of crimps is not particularly limited, it is preferably 2 crimps/25 mm or more and 24 crimps/25 mm or less. If the number of crimps is less than 2/25 mm, the entanglement between the reinforcing fibers and the polyphenylene ether fibers is poor, making it impossible to pass the reinforcing fibers through a carding machine while opening them, making it difficult to form a nonwoven fabric. be.
  • the number of crimps exceeds 24/25 mm, the entanglement of the polyphenylene ether fibers is so strong that the passage through the carding machine becomes poor, and it may become difficult to form a web.
  • the number of crimps of the polyphenylene ether fiber is more preferably 2.5/25 mm or more, still more preferably 3/25 mm or more, and particularly preferably 5/25 mm or more.
  • the number of crimps is more preferably 22/25 mm or less, even more preferably 20/25 mm or less, and particularly preferably 15/25 mm or less. A method for crimping the polyphenylene ether fiber will be described later.
  • the polyphenylene ether fiber is preferably coated with an oil agent, and the amount of the oil agent adhered is preferably 0.03% by mass or more, and preferably 0.05% by mass or more, relative to the mass of the fiber. It is more preferably 0.07% by mass or more, still more preferably 0.08% by mass or more, and particularly preferably 0.1% by mass or more. Also, the upper limit of the amount of oil agent adhered is not particularly limited, but is usually about 5% by mass or less. Since polyphenylene ether fibers are easily electrified, it is preferable to set the oil agent adhesion amount within the above range because electrification can be suppressed when the polyphenylene ether fibers are passed through a carding machine, making it easier to produce a web.
  • the oil agent is not particularly limited, and an oil agent generally used for spinning can be used.
  • Spinning oils impart smoothness and antistatic properties to fibers, and include, for example, water-insoluble oils, water-soluble oils, and emulsifying oils. Among these, water-soluble oils are preferred.
  • the amount of residual solvent in the polyphenylene ether fiber is not particularly limited, but is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and 0.5% by mass or less. It is more preferably not more than 0.1% by mass, and particularly preferably not more than 0.1% by mass. It is preferable from the viewpoint of improving heat resistance that the amount of residual solvent in the polyphenylene ether fiber is within the above range.
  • the fineness of the polyphenylene ether fiber is not particularly limited, and can be appropriately determined according to the purpose for which the fiber is used. is more preferred. When the fineness is within the above range, the entanglement between the fibers becomes strong, and the strength as a nonwoven fabric is improved, which is preferable.
  • the lower limit of fineness is not particularly limited, but it is preferably 0.1 dtex or more, more preferably 0.2 dtex or more.
  • the average fiber length of the polyphenylene ether fiber is not particularly limited, and can be appropriately adjusted depending on the application. be.
  • Reinforcing Fibers are not particularly limited, but examples thereof include carbon fibers, glass fibers, basalt fibers, PBO fibers, and metal fibers.
  • inorganic reinforcing fibers carbon fiber, glass fiber, balsato fiber, metal fiber
  • At least one of the fibers is more preferable.
  • Examples of the carbon fibers include polyacrylonitrile (PAN)-based, pitch-based, and rayon-based carbon fibers.
  • PAN polyacrylonitrile
  • pitch-based pitch-based
  • rayon-based carbon fibers are preferable from the viewpoint of dispersibility with polyphenylene ether fibers.
  • the material of the glass fiber is not particularly limited, and various glass fibers such as E glass, C glass, A glass, S glass, and S-2 glass can be mentioned. Among these, E glass is preferable.
  • the fineness of the reinforcing fiber is not particularly limited, and can be appropriately adjusted according to the application. 100 dtex or less.
  • the average fiber length of the reinforcing fibers is not particularly limited and can be appropriately adjusted depending on the application, but is usually 1 mm or more and 200 mm or less.
  • the average fiber length of the reinforcing fibers is preferably 2 mm or longer, more preferably 5 mm or longer, still more preferably 10 mm or longer, still more preferably 15 mm or longer, and particularly preferably 20 mm or longer. preferable. Also, it is preferably 150 mm or less, more preferably 120 mm or less, and even more preferably 100 mm or less.
  • the average fiber length of the reinforcing fiber is within the above range, the dispersibility with the polyphenylene ether fiber is improved, making it easier to form a uniform nonwoven fabric, which is preferable.
  • the 1% weight loss temperature of the reinforcing fiber of the present invention is preferably 400°C or higher, more preferably 420°C or higher, and even more preferably 450°C or higher. It is preferable that the 1% mass reduction temperature is within the above range because the heat resistance of the obtained nonwoven fabric is improved.
  • the content of the reinforcing fibers in the nonwoven fabric is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Also, the content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. If the fiber content of the reinforcing fibers is less than 10% by mass, the heat resistance and flame retardance of the nonwoven fabric may be inferior, and if it exceeds 90% by mass, the nonwoven fabric may not be formed, which is not preferable.
  • the flame-resistant nonwoven fabric of the present invention contains the flame-resistant polyphenylene ether fiber and the reinforcing fiber, and a sizing agent can be added to improve the interfacial adhesive strength between the flame-resistant polyphenylene ether fiber and the reinforcing fiber.
  • the sizing agent is not particularly limited, and examples thereof include epoxy resins, urethane resins, polyester resins, vinyl ester resins, polyamide resins, polyether resins, acrylic resins, polyolefin resins, polyimide resins, and modified products thereof.
  • a suitable sizing agent can be appropriately selected according to the components of the polyphenylene ether fiber. Moreover, this sizing agent can also be used in combination of two or more. Among these, epoxy resin-based sizing agents are preferred.
  • the amount of the sizing agent added is not particularly limited, it is preferably 0.1 to 5% by mass.
  • nonwoven fabric of the present invention can also contain thermoplastic fibers other than polyphenylene ether within a range that does not impair the effects of the present invention.
  • the nonwoven fabric of the present invention may contain binder fibers in addition to the flame-resistant polyphenylene ether fibers and reinforcing fibers, but may not contain binder fibers in the present invention.
  • the method for producing the flame-resistant nonwoven fabric containing the flame-resistant polyphenylene ether fiber and the reinforcing fiber of the present invention comprises: forming a nonwoven comprising polyphenylene ether fibers and reinforcing fibers; A step of heat-treating the obtained nonwoven fabric in air at 120° C. or higher and 240° C. or lower for 1 hour or longer and 30 hours or shorter to make it infusible; It is characterized by including a step of heat-treating the infusibilized nonwoven fabric in the air at 260° C. or higher and 400° C. or lower for 0.1 hour or longer and 10 hours or shorter to make it flame resistant.
  • the polyphenylene ether fiber, the flameproof polyphenylene ether fiber, and the reinforcing fiber are as described above.
  • a nonwoven fabric containing polyphenylene ether fibers and reinforcing fibers can be formed by a method commonly used in this field.
  • a nonwoven fabric can be formed by forming a web by a carding method using a machine, and subjecting the obtained web to a web fiber bonding treatment such as a needle punch method or a spunlace method.
  • a step of attaching an oil solution to the polyphenylene ether fibers and a step of crimping the polyphenylene ether fibers can be included.
  • the method of attaching the oil agent is not particularly limited, and methods commonly used in this field can be mentioned.
  • the spinning oil can be applied to the polyphenylene ether melt-spun fibers using a gear pump.
  • the ejection amount is not particularly limited, and may be an ejection amount capable of achieving the target oil adhesion amount. It is more preferable to be about 0.015 g/min or more and 0.4 g/min or less.
  • the crimping process is not particularly limited as long as it is a process capable of achieving the desired number of crimps. Examples thereof include false twisting, pressing, gearing, and composite crimping. However, among these, indentation is preferable from the viewpoint of productivity. A preferred number of crimps is as described above.
  • the nonwoven fabric obtained above is subjected to infusibilization treatment and flameproofing treatment.
  • the nonwoven fabric containing polyphenylene ether fibers and reinforcing fibers is treated in the air at 120°C or higher and 220°C or lower for 1 hour or longer and 30 hours or shorter.
  • air means an environment that is not particularly regulated.
  • the treatment temperature is 120° C. or higher, preferably 140° C. or higher, and more preferably 160° C. or higher.
  • the treatment temperature is 240° C. or lower, preferably 230° C. or lower, and more preferably 220° C. or lower.
  • the treatment time is 1 hour or longer, preferably 1.5 hours or longer, and more preferably 2 hours or longer.
  • the treatment time is 30 hours or less, preferably 25 hours or less, and more preferably 23 hours or less.
  • flameproofing treatment is performed in air at 260°C or higher and 400°C or lower for 0.1 hour or longer and 10 hours or shorter.
  • air is an environment that is not specifically conditioned.
  • the treatment temperature is 260° C. or higher, preferably 270° C. or higher, and more preferably 280° C. or higher.
  • the treatment temperature is 400° C. or lower, preferably 380° C. or lower, and more preferably 360° C. or lower.
  • the treatment time is 0.1 hour or longer, preferably 0.3 hour or longer, and more preferably 0.5 hour or longer.
  • the treatment time is 10 hours or less, preferably 8 hours or less, and more preferably 6 hours or less.
  • a non-woven fabric containing polyphenylene ether fibers and reinforcing fibers is subjected to infusibility treatment and flame resistance treatment.
  • Non-woven fabrics can also be formed.
  • the infusibilization treatment and flameproofing treatment of the polyphenylene ether fiber can be carried out by the same methods as those of the nonwoven fabric mentioned above.
  • the reinforcing fibers are as described above.
  • the absorbance height ratio (A/B) is also as described above.
  • Flame-resistant polyphenylene ether is polyphenylene ether that has been flame-resistant. Moreover, the polyphenylene ether may be one containing the aforementioned polyphenylene ether component.
  • the LOI value of the flame-resistant molded product is preferably 46 or more, more preferably 48 or more, and even more preferably 50 or more.
  • the LOI value is the limiting oxygen index, and the larger the LOI value, the more excellent the flame retardancy. Therefore, the larger the LOI value, the better, and the upper limit is not particularly limited.
  • the deflection temperature under load of the flame-resistant molded article under a load of 1.80 MPa is preferably 250°C or higher, more preferably 280°C or higher, and even more preferably 300°C or higher.
  • the shape of the flame-resistant molded article is not particularly limited, and can be appropriately determined according to the purpose for which the flame-resistant molded article is used. and can be formed into the required shape using a mold.
  • the thickness is not particularly limited and can be appropriately determined according to the purpose for which the molded product is used. It is more preferable to be about 0.05 mm or more and 80 mm or less.
  • the mass ratio of the polyphenylene ether and the reinforcing fiber contained in the molded article of the present invention is not particularly limited, and can be appropriately determined according to the purpose for which the molded article is used. , more preferably about 90/10 or more and 10/90 or less, and even more preferably about 60/40 or more and 40/60 or less.
  • the content of the flame-resistant polyphenylene ether in the flame-resistant molded article of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the flame-resistant molded article. Moreover, it is preferably 95% by mass or less, more preferably 90% by mass or less, relative to the total amount of the molded product.
  • the content of the flame-resistant polyphenylene ether is within the above range, both flame retardancy and strength can be achieved, which is preferable.
  • the content of the reinforcing fiber in the flame-resistant molded article of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the flame-resistant molded article. Moreover, it is preferably 90% by mass or less, more preferably 95% by mass or less, relative to the total amount of the molded product. It is preferable that the content of the reinforcing fiber is within the above range, because excellent mechanical strength is exhibited.
  • the molded article of the present invention contains flame-resistant polyphenylene ether and reinforcing fibers, but may contain other components.
  • the content of other components is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably not contained (0% by mass) relative to the total amount of the molded product.
  • the same components as those that can be contained in the above-described nonwoven fabric can be mentioned.
  • the method for producing the flame-resistant molded article of the present invention is not particularly limited, and the molded article can be produced by pressing and molding a non-woven fabric containing polyphenylene ether fibers and reinforcing fibers and subjecting the molded article to the above-mentioned flame-resistant treatment. Specifically, it can be produced satisfactorily by the method for producing a flame-resistant molded article of the present invention, which will be described later.
  • the method for producing a flame-resistant molded article containing flame-resistant polyphenylene ether and reinforcing fibers comprises a step of pressing a non-woven fabric containing polyphenylene ether fibers and reinforcing fibers to form a molded article.
  • a step of heat-treating the molded body in the air at 120° C. or more and 240° C. or less for 1 hour or more and 30 hours or less to make it infusible (infusibilization treatment); It is characterized by including a step of flameproofing by heat treatment at 400° C. or less for 0.1 hour or more and 10 hours or less (flameproof treatment).
  • the non-woven fabric containing polyphenylene ether fiber and reinforcing fiber, infusibilization treatment, and flameproofing treatment are as described above.
  • the pressing temperature is not particularly limited, but is preferably 260°C or higher, more preferably 280°C or higher.
  • the upper limit is not particularly limited, but is preferably 420° C. or lower, more preferably 400° C. or lower.
  • the pressing pressure is not particularly limited, it is preferably 0.5 MPa or higher, more preferably 1 MPa or higher. Moreover, it is preferably 50 MPa or less, more preferably 40 MPa or less. By setting the press working pressure within the above range, the gaps between the reinforcing fibers are sufficiently impregnated with the resin, which is preferable.
  • the pressing time is not particularly limited, but is preferably 0.5 seconds or longer, more preferably 10 seconds or longer, and even more preferably 30 seconds or longer. Also, it is preferably 1200 seconds or less, more preferably 600 seconds or less. By setting the press working time within the above range, it is possible to achieve both impregnation of the resin between the reinforcing fibers and suppression of thermal deterioration, which is preferable.
  • the press working can be performed by a method commonly used in this field.
  • the flame-resistant nonwoven fabric and the flame-resistant molded product of the present invention can be used, for example, in sound absorbing materials for automobiles, interior materials for automobiles, heat insulating materials, fire extinguishing cloths for home use, fireproof covers, surface materials for ducts, plastic flameproof materials, fire spread prevention materials, and dust. It can be used for scattering prevention surface materials, cement reinforcing materials, friction materials, gland packing, sealing materials, firefighting clothing, welding spark protection sheets, etc., but in particular, fields such as aerospace materials that require a high level of flame resistance. Can be preferably used in.
  • thermogravimetry device model: TGA Q50 manufactured by TA Instruments Co., Ltd.
  • 10 mg of reinforcing fiber is packed in a platinum pan and heated from 20 ° C. to 900 ° C. at 20 ° C./min. The temperature was measured when the mass decreased by 1%.
  • Thickness 20 arbitrary locations were selected and measured with a constant pressure thickness measuring instrument (7 gf/cm 2 ) manufactured by Ozaki Seisakusho Co., Ltd.).
  • Weight per unit area Measured according to JIS L1906 (2000) 5.2 mass per unit area.
  • LOI value flame retardant It was measured according to JIS L 1091 E method. The oxygen index was determined when combustion continued for 50 mm or more, and propane gas was used as the heat source of the igniter.
  • glass transition temperature (Tg) glass transition temperature (Tg) Using a differential scanning calorimeter (model: DSC-Q100) manufactured by TA Instruments Co., Ltd., 2 mg of fiber is measured from 30 ° C. to 250 ° C. in a nitrogen atmosphere at a temperature increase rate of 10 ° C./min, The temperature at the intersection of the extended line of the baseline below the glass transition temperature and the tangent line showing the maximum slope at the transition portion was defined as the glass transition temperature (Tg).
  • Example 1 Poly (2,6-dimethyl-1,4-phenylene ether) (PPO640, glass transition temperature (Tg): 221 ° C., manufactured by SABIC Innovative Plastic), a twin-screw extruder manufactured by Technobell Co., Ltd. (product name: KZW15TW) -30 MG).
  • the twin-screw extruder the cylinder has 4 zones, the cylinders are respectively cylinders 1, 2, 3, and 4 from the hopper side, cylinders 1 to 3 are set to 290 ° C., cylinder 4 and cylinder head The part was set to 310° C., the screw rotation speed was set to 700 rpm, and the peripheral speed of the screw was set to 33.0 m/min.
  • a gear pump is installed downstream of the extruder, and a nozzle (nozzle hole diameter: 0.50 mm, nozzle hole land length: 1 .0 mm, number of nozzle holes: 24) (total discharge amount: 12.64 g/min).
  • the polymer discharged from the nozzle was wound up at a spinning speed of 1053 m/min.
  • a gear pump with a capacity of 0.06 cc/rev was used to apply a spinning oil (discharge rate: 0.36 g/min), and the amount of oil applied to the obtained fiber was 0.2% by mass. rice field.
  • the resulting fiber had a dislocation structure (amount of dislocation structure: 2.8 mol % with respect to the total PPE units) and had a glass transition temperature of 205°C.
  • Polyphenylene ether fibers were combined to 10000 dtex and crimped with a commercially available crimper to produce a polyphenylene ether staple.
  • the crimping process was performed by heating to 100° C. or higher with steam.
  • PAN-based carbon fiber with an average fiber length of 50 mm obtained by opening a carbon fiber bundle (product name: T700, filament diameter: 7 ⁇ m, 1% mass loss temperature: 520 ° C., manufactured by Toray Industries, Inc.) 52% by mass and an average fiber length of 51 mm
  • a carbon fiber bundle product name: T700, filament diameter: 7 ⁇ m, 1% mass loss temperature: 520 ° C., manufactured by Toray Industries, Inc.
  • carding was performed with a commercially available carding machine to form a web, and the fibers were entangled by a needle punch method to form a nonwoven fabric.
  • the obtained nonwoven fabric had a thickness of 2.6 mm and a basis weight of 250 g/m 2 .
  • Example 2 A flame-resistant nonwoven fabric was produced in the same manner as in Example 1, except that the reinforcing fiber mass content was 40% by mass. Each evaluation result is shown in Table 1.
  • Example 3 In the same manner as in Example 1, except that glass fibers with an average fiber length of 70 mm (E glass, filament diameter: 10 ⁇ m, 1% mass loss temperature: >500 ° C., Nitto Boseki Co., Ltd.) were used as reinforcing fibers. A modified nonwoven fabric was produced. Each evaluation result is shown in Table 1.
  • Example 4 A flame-resistant nonwoven fabric was produced in the same manner as in Example 3, except that the reinforcing fiber mass content was 40% by mass. Each evaluation result is shown in Table 1.
  • Comparative example 1 A flame-resistant nonwoven fabric was produced in the same manner as in Example 1 except that a nonwoven fabric produced using only the polyphenylene ether fibers obtained in Example 1 without containing carbon fibers was used, and various evaluations were performed. Each evaluation result is shown in Table 1.
  • Comparative example 2 A nonwoven fabric was produced in the same manner as in Example 1, except that the flameproofing treatment was not performed, and various evaluations were performed. Each evaluation result is shown in Table 1.
  • Comparative example 3 Carding of PAN-based carbon fibers (product name: T700, filament diameter: 7 ⁇ m, 1% mass loss temperature: 520° C., manufactured by Toray Industries, Inc.) with an average fiber length of 50 mm obtained by opening a carbon fiber bundle using a commercially available carding machine. After being processed into a web by doing so, the fibers were entangled by a needle punching method to form a nonwoven fabric.
  • Example 5 A crimped polyphenylene ether fiber was prepared in the same manner as in Example 1.
  • PAN-based carbon fiber with an average fiber length of 70 mm (product name: T700, filament diameter: 7 ⁇ m, 1% mass loss temperature: 520 ° C., manufactured by Toray Industries, Inc.) obtained by opening a carbon fiber bundle 52% by weight and an average fiber length of 51 mm
  • T700 filament diameter
  • 1% mass loss temperature 520 ° C.
  • carding was performed with a commercially available carding machine to form a web, and the fibers were entangled by a needle punch method to form a nonwoven fabric.
  • the fiber mass ratio of the carbon fibers was 52% by mass
  • the thickness of the obtained nonwoven fabric was 2.8 mm
  • the basis weight was 300 g/m 2 .
  • the non-woven fabrics were layered so as to have a basis weight of 3000 g/m 2 and were compression-molded with a heat press at 350° C. under a pressure of 10 MPa for 2 minutes to form a flat plate.
  • Example 6 A flame-resistant nonwoven fabric was produced in the same manner as in Example 5, except that the reinforcing fiber mass content was 40% by mass. Each evaluation result is shown in Table 1.
  • Example 7 In the same manner as in Example 5, except that the reinforcing fibers were glass fibers with an average fiber length of 70 mm (E glass, filament diameter: 10 ⁇ m, 1% mass loss temperature: >500 ° C., Nitto Boseki Co., Ltd.). A modified nonwoven fabric was produced. Each evaluation result is shown in Table 1.
  • Comparative example 4 A molded body was produced in the same manner as in Example 3 except that the infusible and flameproofing treatments were not performed, and various evaluations were performed. Each evaluation result is shown in Table 2.
  • Comparative example 5 A molded body was produced in the same manner as in Comparative Example 4 except that the carbon fiber was not mixed, and various evaluations were performed. Each evaluation result is shown in Table 2.
  • Comparative example 6 The molding obtained in Comparative Example 5 was treated for flame resistance in the same manner as in Example 3, but the shape could not be maintained and evaluation could not be performed.
  • the flame-resistant molded article of the present invention has an LOI value of 55 or more, indicating that it has extremely high flame retardancy.
  • the deflection temperature under load was 300° C. or higher, indicating that it had high heat resistance.
  • Comparative Example 4 which was not subjected to flameproofing treatment
  • Comparative Example 5 which did not contain carbon fiber and was not subjected to flameproofing treatment
  • both flame retardancy and heat resistance were insufficient.
  • Comparative Example 6 in which a molded body containing no carbon fiber was subjected to a flameproofing treatment, the shape of the molded body could not be maintained.

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PCT/JP2022/048253 2022-01-17 2022-12-27 耐炎化ポリフェニレンエーテル繊維及び補強繊維を含む耐炎化不織布、耐炎化ポリフェニレンエーテル及び補強繊維を含む耐炎化成型体、並びにそれらの製造方法 WO2023136141A1 (ja)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2025004855A1 (ja) * 2023-06-27 2025-01-02 東洋紡エムシー株式会社 捲縮ポリフェニレンエーテル繊維、不織布、成型体、耐炎化不織布、耐炎化成型体、並びに捲縮ポリフェニレンエーテル繊維及び不織布の製造方法

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Publication number Priority date Publication date Assignee Title
JPH0457949A (ja) * 1990-06-25 1992-02-25 Kawasaki Steel Corp ピッチ系炭素繊維を主成分とする混紡フェルトの製造方法
JP2002266217A (ja) * 2001-03-08 2002-09-18 Mitsubishi Rayon Co Ltd 炭素繊維不織布およびその製造方法
JP2006104643A (ja) * 2004-09-08 2006-04-20 Osaka Gas Chem Kk 混紡フェルトおよび炭素繊維フェルト
WO2021111707A1 (ja) * 2019-12-03 2021-06-10 東洋紡株式会社 耐炎化ポリフェニレンエーテル成形体、及び、耐炎化ポリフェニレンエーテル成形体の製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH0457949A (ja) * 1990-06-25 1992-02-25 Kawasaki Steel Corp ピッチ系炭素繊維を主成分とする混紡フェルトの製造方法
JP2002266217A (ja) * 2001-03-08 2002-09-18 Mitsubishi Rayon Co Ltd 炭素繊維不織布およびその製造方法
JP2006104643A (ja) * 2004-09-08 2006-04-20 Osaka Gas Chem Kk 混紡フェルトおよび炭素繊維フェルト
WO2021111707A1 (ja) * 2019-12-03 2021-06-10 東洋紡株式会社 耐炎化ポリフェニレンエーテル成形体、及び、耐炎化ポリフェニレンエーテル成形体の製造方法

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Publication number Priority date Publication date Assignee Title
WO2025004855A1 (ja) * 2023-06-27 2025-01-02 東洋紡エムシー株式会社 捲縮ポリフェニレンエーテル繊維、不織布、成型体、耐炎化不織布、耐炎化成型体、並びに捲縮ポリフェニレンエーテル繊維及び不織布の製造方法

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