WO2025009443A1 - Fibre unique d'aramide longue-fine, son procédé de fabrication, et matériau composite et feuille contenant une fibre unique d'aramide longue-fine - Google Patents

Fibre unique d'aramide longue-fine, son procédé de fabrication, et matériau composite et feuille contenant une fibre unique d'aramide longue-fine Download PDF

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Publication number
WO2025009443A1
WO2025009443A1 PCT/JP2024/023019 JP2024023019W WO2025009443A1 WO 2025009443 A1 WO2025009443 A1 WO 2025009443A1 JP 2024023019 W JP2024023019 W JP 2024023019W WO 2025009443 A1 WO2025009443 A1 WO 2025009443A1
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Prior art keywords
aramid
long
fibers
fine
fiber
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PCT/JP2024/023019
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English (en)
Japanese (ja)
Inventor
竜太 岩浦
雄輝 大川
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Tokushu Tokai Paper Co Ltd
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Tokushu Tokai Paper Co Ltd
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Priority to KR1020257041390A priority Critical patent/KR20260035817A/ko
Priority to CN202480041849.5A priority patent/CN121420100A/zh
Publication of WO2025009443A1 publication Critical patent/WO2025009443A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D04H1/4334—Polyamides
    • D04H1/4342—Aromatic polyamides
    • 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 very thin and long aramid monofilaments, and to their production and use.
  • Aromatic polyamides include para-aromatic polyamides such as polyparaphenylene terephthalamide, and meta-aromatic polyamides such as polymetaphenylene isophthalamide, both of which are used as fibers.
  • Patent Document 1 describes the production of aramid nanofibers with an average fiber diameter of 20 nm by discharging a solution of aramid in the strong base dimethyl sulfoxide into water and spinning it (see Patent Document 1, paragraphs [0051] to [0053]).
  • the aramid nanofibers obtained by the method described in Patent Document 1 are relatively short and have low crystallinity.
  • the objective of the present invention is to provide aramid single fibers that are extremely thin, long, and highly crystallized.
  • the average fiber diameter of the long fine aramid single fibers is preferably less than 1000 nm.
  • the average aspect ratio of the long fine aramid single fibers is 100 or more.
  • the glass transition temperature of the long fine aramid single fibers is preferably greater than 300°C.
  • the aramid constituting the long fine aramid monofilaments is preferably meta-aramid.
  • a second aspect of the present invention is A swelling step of bringing raw material aramid fibers having a soluble content in dimethyl sulfoxide of 10% by mass or more into contact with a swelling liquid containing an aprotic solvent to cause the fibers to swell;
  • the method for producing the long fine aramid single fibers includes a separation step of separating long fine aramid single fibers having a fiber diameter of less than 2000 nm and a fiber length of more than 10 ⁇ m from the fine raw material aramid fibers.
  • the aprotic solvent is preferably dimethylsulfoxide and/or dimethylacetamide.
  • the glass transition point of the long fine aramid single fibers is 30°C or more higher than the glass transition point of the raw aramid fibers.
  • the third aspect of the present invention is a composite material containing the above-mentioned long fine aramid monofilaments and a matrix resin.
  • the long fine aramid fibers are dispersed in the matrix resin.
  • the matrix resin is preferably an epoxy resin.
  • the fourth aspect of the present invention is a sheet containing the above-mentioned long fine aramid monofilaments.
  • the long fine aramid single fibers of the present invention are extremely thin, long, and highly crystallinity.
  • the manufacturing method of the long and fine aramid single fibers of the present invention can produce aramid fibers that are very thin, long, and have a high degree of crystallinity. Furthermore, the manufacturing method of the long and fine aramid single fibers of the present invention is highly productive and is advantageous for the industrial production of long and fine aramid single fibers.
  • the composite material or sheet of the present invention can exhibit properties derived from the long, fine aramid monofilaments contained therein.
  • the following describes the long fine aramid single fibers of the present invention, the method for producing the long fine aramid single fibers, and the composite material or sheet containing the long fine aramid single fibers.
  • aromatic polyamide refers to an aromatic polyamide.
  • aromatic polyamide refers to a linear polymer compound in which, in terms of chemical structure, 60 mol % or more, preferably 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more of amide bonds are directly bonded to aromatic rings.
  • Aramids are classified into para-aramids, meta-aramids and their copolymers depending on the substitution position of the amide group on the benzene ring.
  • para-aramids include polyparaphenylene terephthalamide and its copolymers, poly(paraphenylene)-copoly(3,4'-diphenyl ether) terephthalamide (poly(paraphenylene)-copoly(3,4'-diphenyl ether) terephthalamide), etc.
  • meta-aramids include polymetaphenylene isophthalamide and its copolymers.
  • Meta-aramids are industrially produced, for example, by conventionally known interfacial polymerization methods, solution polymerization methods, etc., and are available as commercial products, but are not limited thereto.
  • meta-aramids are preferably selected. Meta-aramids have the following characteristics: they are soluble in general-purpose amide solvents, can be wet molded using a polymer solution as the starting material, have excellent heat fusion adhesion, and have good heat resistance and flame retardancy.
  • polymetaphenylene isophthalamide is preferably used because it has good moldability, heat adhesion, flame retardancy, heat resistance, and other properties.
  • the long fine aramid monofilament of the present invention is a monofilament.
  • the term "monofilament” means a fiber without branches, and does not mean a fiber with branches such as a fibrillated fiber.
  • the long fine aramid single fibers of the present invention are very thin (i.e., fine) fibers with a maximum fiber diameter of less than 2000 nm.
  • the maximum fiber diameter of the long fine aramid single fibers of the present invention is preferably less than 1900 nm, more preferably less than 1800 nm, and even more preferably less than 1700 nm.
  • the maximum fiber diameter of the long fine aramid single fibers of the present invention may be 1000 nm or more.
  • the long fine aramid single fibers of the present invention preferably have a minimum fiber diameter of more than 100 nm, more preferably more than 150 nm, and even more preferably more than 200 nm.
  • the minimum fiber diameter of the long fine aramid single fibers of the present invention is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the long fine aramid single fibers of the present invention preferably have an average fiber diameter of less than 1000 nm, more preferably less than 950 nm, and even more preferably less than 900 nm.
  • the long fine aramid single fibers of the present invention preferably have an average fiber diameter of more than 400 nm, more preferably more than 500 nm, and even more preferably more than 600 nm.
  • the average fiber diameter of the long fine aramid single fibers of the present invention is preferably more than 400 nm but less than 1000 nm, more preferably more than 500 nm but less than 950 nm, and even more preferably more than 600 nm but less than 900 nm.
  • the maximum fiber diameter, minimum fiber diameter, and average fiber diameter of the long fine aramid single fiber of the present invention can be determined for a set of a predetermined number of fibers. Specifically, the fiber diameters of 100 long fine aramid single fibers of the present invention are measured by observation with an electron microscope such as an SEM, and the maximum fiber diameter and the minimum fiber diameter are taken as the maximum and minimum fiber diameters, respectively, and the number average value of the fiber diameters can be taken as the average fiber diameter.
  • the long fine aramid single fibers of the present invention are relatively long fibers having a minimum fiber length of more than 10 ⁇ m.
  • the minimum fiber length of the long fine aramid single fibers of the present invention is preferably more than 20 ⁇ m, more preferably more than 30 ⁇ m, more preferably more than 40 ⁇ m, more preferably more than 50 ⁇ m, and even more preferably more than 60 ⁇ m.
  • the upper limit of the minimum fiber length of the long fine aramid single fibers of the present invention is not particularly limited, but can be, for example, less than 100 ⁇ m.
  • the maximum fiber length of the long fine aramid single fibers of the present invention is preferably less than 1000 ⁇ m, more preferably less than 800 ⁇ m, and even more preferably less than 600 ⁇ m.
  • the maximum fiber length of the long fine aramid single fibers of the present invention is preferably 200 ⁇ m or more, more preferably 250 ⁇ m or more, and even more preferably 300 ⁇ m or more.
  • the average fiber length of the long fine aramid single fibers of the present invention is preferably more than 20 ⁇ m, more preferably more than 50 ⁇ m, and even more preferably more than 80 ⁇ m.
  • the average fiber length of the long fine aramid single fibers of the present invention is preferably less than 400 ⁇ m, more preferably less than 300 ⁇ m, and even more preferably less than 200 ⁇ m.
  • the average fiber length of the long fine aramid single fibers of the present invention is preferably more than 20 ⁇ m but less than 400 ⁇ m, preferably more than 50 ⁇ m but less than 300 ⁇ m, and even more preferably more than 80 ⁇ m but less than 200 ⁇ m.
  • the minimum fiber length, maximum fiber length, and average fiber length of the long fine aramid single fiber of the present invention can be determined for a set of a specified number of fibers. Specifically, the fiber lengths of 100 long fine aramid single fibers of the present invention can be measured by observation with an electron microscope such as an SEM, and the minimum fiber length and the maximum fiber length can be determined as the minimum fiber length and the maximum fiber length, respectively, and the number average value of the fiber lengths can be determined as the average fiber length.
  • the long and fine aramid single fibers of the present invention are fibers with a relatively high aspect ratio.
  • the minimum aspect ratio of the long and fine aramid single fibers of the present invention is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more.
  • the maximum aspect ratio of the long and fine aramid single fibers of the present invention is not particularly limited, but can be, for example, less than 500.
  • the average aspect ratio of the long and fine aramid single fibers of the present invention is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.
  • the upper limit of the average aspect ratio of the long and fine aramid single fibers of the present invention is not particularly limited, but can be, for example, less than 400.
  • the minimum aspect ratio, maximum aspect ratio, and average aspect ratio of the long fine aramid single fibers of the present invention can also be determined for a set of a specified number of fibers. Specifically, the fiber lengths of 100 long fine aramid single fibers of the present invention are measured by observation with an electron microscope such as an SEM, and the aspect ratio of each fiber is determined from the fiber length and fiber diameter of each fiber. The smallest of these is defined as the minimum aspect ratio, and the largest is defined as the maximum aspect ratio, and the number average of these is defined as the average aspect ratio.
  • the long and fine aramid single fiber of the present invention has a relatively high crystallinity.
  • x (1- ⁇ Qx/ ⁇ Q 0 ) ⁇ 100(%)
  • ⁇ Qx is the amount of change in heat capacity before and after the glass transition point of the long fine aramid single fiber of the present invention
  • the crystallinity x determined by the above method ( ⁇ Q0 is the amount of change in heat capacity before and after the glass transition point of amorphous aramid) is 60% or more.
  • the crystallinity of the long fine aramid single fibers of the present invention is preferably 70% or more, and more preferably 80% or more. There is no particular upper limit to the crystallinity of the long fine aramid single fibers of the present invention, but it can be, for example, 95% or less or 90% or less.
  • amorphous aramid an aramid that is completely soluble in dimethyl sulfoxide (in the absence of a base) at room temperature (25°C) can be used.
  • the baseline shift interval can be determined by linearly approximating the baseline.
  • the long fine aramid single fiber of the present invention preferably has a glass transition point of over 300°C, more preferably over 310°C, and even more preferably over 320°C.
  • a high glass transition point means that there are fewer amorphous parts that undergo Brownian motion, and the crystallinity is high.
  • the long, fine aramid single fibers of the present invention are single fibers that are unbranched, and therefore have excellent mixability with resins, etc.
  • the long fine aramid single fibers of the present invention are fine, but also relatively long, so they can exhibit superior mechanical properties when composited with resins, etc.
  • the long, fine aramid single fibers of the present invention have high crystallinity, so the fiber shape is stable and can be well maintained against various physical or chemical effects.
  • the method for producing the long fine aramid single fibers of the present invention comprises the steps of: A swelling step of bringing raw material aramid fibers having a soluble content in dimethyl sulfoxide of 10% by mass or more into contact with a swelling liquid containing an aprotic solvent to cause the fibers to swell; A mechanical defibration step of finely pulverizing the raw aramid fibers by mechanical defibration; and The method includes a separation step of separating long fine aramid single fibers having a fiber diameter of less than 2000 nm and a fiber length of more than 10 ⁇ m from the finely divided raw aramid fibers.
  • the method for producing long, fine aramid single fibers of the present invention is characterized in that, instead of spinning an aramid solution, a specified raw material aramid fiber is swelled and mechanically defibrated to form single fibers.
  • the method for producing long, fine aramid single fibers of the present invention can produce aramid fibers that are very thin, long, and highly crystallized.
  • the method for producing long, fine aramid single fibers of the present invention is capable of achieving high productivity and is industrially advantageous.
  • aramid single fibers can be produced by electrospinning, but electrospinning has low productivity and is disadvantageous for industrial production.
  • aramid fibers having a dimethyl sulfoxide soluble content of 10% by mass (weight) or more are used as a raw material.
  • the soluble content of the raw material aramid fibers is based on the total mass (total weight) of the raw material aramid fibers.
  • aramid fiber having a soluble content in dimethyl sulfoxide of 10 mass (weight) % or more aramid fiber that changes in mass (weight) by 10% or more when immersed in dimethyl sulfoxide (with a purity of 99.5% or more and containing no bases such as sodium hydroxide or potassium hydroxide) at room temperature (25°C) for 72 hours can be used.
  • a raw aramid fiber having a dimethyl sulfoxide soluble content of 10% by mass (weight) or more has a tendency for the amorphous portion to be solvated, and the fiber to swell easily.
  • the dimethyl sulfoxide soluble content of the raw aramid fiber is not particularly limited as long as it is 10% by mass (weight) or more, but may be, for example, 15% by mass (weight) or more, 20% by mass (weight) or more, 25% by mass (weight) or more, or 30% by mass (weight) or more.
  • the dimethyl sulfoxide soluble content of the raw aramid fiber is preferably 80% by mass (weight) or less, more preferably 70% by mass (weight) or less, and even more preferably 60% by mass (weight) or less.
  • the form of the raw aramid fiber is not particularly limited, and either branched or unbranched fibers can be used.
  • the raw aramid fiber may be in the form of aramid flock or aramid fibrids.
  • the (number) average fiber length of the aramid flock is not particularly limited, but can be, for example, in the range of 1 to 50 mm, preferably in the range of 2 to 40 mm, and more preferably in the range of 3 to 30 mm.
  • the (number) average fiber diameter of the aramid flock is also not particularly limited, but can be, for example, in the range of 10 to 30 ⁇ m, preferably in the range of 12 to 28 ⁇ m, and more preferably in the range of 14 to 26 ⁇ m.
  • the average fiber length and average fiber diameter of aramid flock can be obtained by averaging the lengths and widths of a certain number of aramid flocks (e.g., 100 flocks). Specifically, the fiber lengths and fiber diameters of 100 flocks of aramid flock can be measured by observation with an electron microscope such as a SEM, and the average fiber length can be taken as the average fiber length, and the average fiber diameter can be taken as the average fiber diameter.
  • “Aramid fibrids” are film-like or fibrous microparticles made of aramid, and are sometimes called aramid pulp (for more on aramid fibrids, see JP-B-35-11851 and JP-B-37-5752, etc.). Since fibrids have the same papermaking properties as regular wood (cellulose) pulp, they can be dispersed in water and then molded into a sheet using a papermaking machine.
  • the (number) average fiber diameter of the aramid fibrids is not particularly limited, but can be, for example, 4 to 40 ⁇ m, preferably 5 to 35 ⁇ m, and more preferably 6 to 30 ⁇ m.
  • the average fiber diameter of aramid fibrids can be obtained by averaging the widths of a certain number of aramid fibrids (e.g., 100 fibers). Specifically, the fiber diameters of 100 fibers of aramid fibrids can be measured by observation with an electron microscope such as SEM, and the average value of the fiber diameters can be used as the average fiber diameter.
  • the aprotic solvent is not particularly limited as long as it is capable of swelling the raw aramid fiber, but dimethyl sulfoxide, dimethyl acetamide, or a mixture of the two can be preferably used.
  • the aprotic solvent breaks the hydrogen bonds between the less crystalline parts of the raw aramid fiber, making it easier to separate the more crystalline parts excluding those parts as fine fibers.
  • the swelling liquid may contain optional components other than the aprotic solvent, such as acids, bases, salts, water, etc., as necessary.
  • the amount of the optional components is not particularly limited, but may be, for example, 0.001 to 10% by mass (weight), 0.01 to 5% by mass (weight), or 0.1 to 1% by mass (weight) based on the total mass (total weight) of the swelling liquid.
  • the manner in which the raw aramid fibers are brought into contact with the swelling liquid is not particularly limited, and for example, the raw aramid fibers can be immersed in the swelling liquid, or the swelling liquid can be sprinkled or sprayed onto the raw aramid fibers.
  • the manner in which the raw aramid fibers are immersed in the swelling liquid is preferred.
  • the contact temperature and contact time are not particularly limited as long as the raw aramid fibers swell, and can be, for example, in the range of room temperature (25°C) to 40°C and 10 minutes to 1 hour.
  • the raw aramid fiber swelled during the swelling process is then sent to the mechanical defibration process.
  • Mechanical defibration can be carried out by any known method as long as the defibration is mechanical. It is preferable that mechanical defibration be carried out by applying a shear force to the swollen raw aramid fiber.
  • the equipment used for mechanical fiberization is not particularly limited, and examples that can be used include devices that apply collision shear forces such as planetary ball mills and bead mills, devices that apply rotational shear forces such as disc refiners and grinders, devices capable of highly efficient kneading, stirring and dispersion such as various kneaders and planetary mixers, high-pressure homogenizers, etc. It is preferable to use a Clearmix device (for example, one manufactured by MTECHNIQUE) equipped with a high-speed rotating rotor and a screen arranged with a small clearance.
  • a Clearmix device for example, one manufactured by MTECHNIQUE
  • long fine aramid single fibers with a fiber diameter of less than 2000 nm and a fiber length of more than 10 ⁇ m are separated from the fine fibers separated from the raw aramid fibers in the mechanical fiberization process.
  • the separation method is not particularly limited, and can be performed by a known method.
  • the raw aramid fibers that have been finely divided in the mechanical fiberization process can be diluted and then centrifuged, and the supernatant liquid can be filtered to separate long fine aramid single fibers having a fiber diameter of less than 2000 nm and a fiber length of more than 10 ⁇ m from the raw aramid fibers.
  • the dilution medium (liquid) is preferably an aprotic solvent.
  • aprotic solvent dimethyl sulfoxide, dimethylacetamide, or a mixture of the two can be preferably used.
  • the dilution medium may contain optional components other than the aprotic solvent, such as acids, bases, salts, and water, as necessary.
  • the amount of the optional components is not particularly limited, but may be, for example, 0.001 to 10% by weight, 0.01 to 5% by weight, or 0.1 to 1% by weight based on the total mass (total weight) of the dilution medium (liquid).
  • the long and fine aramid single fibers of the present invention can be obtained by the manufacturing method of the long and fine aramid single fibers of the present invention.
  • the method for producing long and fine aramid single fibers of the present invention can produce long and fine aramid single fibers of the present invention having a glass transition point that is 30°C or more higher than the glass transition point of the raw aramid fibers.
  • a high glass transition point means that there are fewer amorphous parts that undergo Brownian motion and the crystallinity is high. Therefore, the method for producing long and fine aramid single fibers of the present invention can produce long and fine aramid single fibers that have a higher degree of crystallinity than the raw aramid fibers.
  • the present invention also relates to a composite material or sheet containing the above-mentioned long fine aramid monofilaments.
  • the composite material of the present invention contains the above-mentioned long fine aramid monofilaments and a matrix resin.
  • the long fine aramid single fibers are preferably dispersed in the matrix resin. Since the long fine aramid single fibers are not branched, they can be easily mixed with the matrix resin. In addition, since the long fine aramid single fibers are relatively long, it is easy to increase the mechanical strength of the composite material.
  • the matrix resin is not particularly limited, and a thermoplastic resin, a thermosetting resin, or a mixture of both can be used.
  • thermoplastic resin is not particularly limited, and one or more of polyolefin resin, nylon resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyetherimide resin, polyether ketone resin, etc. can be used.
  • thermosetting resin is not particularly limited, and one or more of epoxy resin, unsaturated polyester resin, vinyl ester resin, etc. can be used. Epoxy resin is preferred.
  • the mass (weight) ratio of the matrix resin to the long fine aramid single fibers is preferably 50/50 to 90/10, more preferably 55/45 to 80/20, and particularly preferably 60/40 to 70/30, from the viewpoint of the strength of the composite material.
  • the composite material of the present invention can be obtained, for example, by adding the long fine aramid single fibers to a molten thermoplastic matrix resin, mixing and kneading the mixture, and then subjecting the mixture to extrusion molding or injection molding.
  • the composite material of the present invention can be obtained, for example, by mixing the long fine aramid monofilaments with the matrix resin and molding them under heat.
  • the composite material does not need to be completely cured, but it is preferable that the molded composite material is cured to an extent that it can maintain its shape. After molding, it may be further heated to completely cure.
  • the composite material of the present invention can have a higher dielectric strength than the matrix resin itself. Therefore, the composite material of the present invention can be suitably used as an electrical insulator.
  • the composite material of the present invention can have a higher glass transition point than the glass transition point of the matrix resin itself. Therefore, the composite material of the present invention has a more stable shape than the matrix resin, and can be suitably used in a variety of applications.
  • the sheet of the present invention contains the above-mentioned long fine aramid monofilaments.
  • the sheet of the present invention containing the above-mentioned long fine aramid monofilaments can exhibit excellent strength, electrical insulation, etc.
  • the sheet of the present invention is preferably porous.
  • the form of the sheet of the present invention is not particularly limited, and various forms such as woven fabric, nonwoven fabric, and paper can be used, but the form of nonwoven fabric or paper is preferable.
  • the thickness of the sheet of the present invention is preferably 1 to 300 ⁇ m, more preferably 2 to 200 ⁇ m, and even more preferably 3 to 100 ⁇ m.
  • the basis weight of the sheet of the present invention is preferably 10 to 500 g/ m2 , more preferably 20 to 400 g/ m2 , and even more preferably 30 to 300 g/ m2 .
  • the sheet of the present invention preferably contains 50 to 99% by mass (weight) of the long fine aramid monofilaments, more preferably 60 to 95% by mass (weight), and even more preferably 70 to 90% by mass (weight) of the total mass (total weight) of the sheet.
  • the sheet of the present invention is preferably composed mainly of the above-mentioned long fine aramid fibers (80% by mass (weight) or more of the total mass).
  • the sheet of the present invention mainly contains the above-mentioned long fine aramid single fibers, it is easy to reduce the thickness of the sheet and obtain a very thin sheet.
  • the sheet of the present invention can be produced, for example, by forming the long fine aramid single fibers into a sheet by a known method. Specifically, for example, a method of dispersing the long fine aramid single fibers, if necessary together with other fibers, in a dry state to form a sheet; a method of dispersing and mixing the long fine aramid single fibers, if necessary together with other fibers, in a liquid medium such as water to obtain a slurry, discharging the slurry onto a liquid-permeable support such as a net or belt to form a sheet, and then removing the liquid medium and drying the slurry can be used.
  • a liquid medium such as water
  • a liquid-permeable support such as a net or belt
  • an aqueous slurry containing at least the above-mentioned long fine aramid single fibers is generally fed to a papermaking machine, dispersed, dehydrated, squeezed out, and dried, and then wound into a sheet (wet papermaking method).
  • Papermaking machines that can be used include Fourdrinier papermaking machines, cylinder papermaking machines, tilted papermaking machines, and combination papermaking machines that combine these. Additives such as dispersibility improvers, defoamers, and paper strength enhancers are used as necessary during papermaking.
  • Example 1 Preparation of long and fine aramid single fibers 2 g of raw aramid fibers were dried in an oven at 105° C. for 24 hours, put into 198 g of dimethyl sulfoxide to swell, and then decomposed for 60 minutes in a homomixer (Primix Corporation, MARKII2.5 type) at 10,000 rpm. This was then decomposed for 20 minutes in a clear mixer (M Technique Corporation, CLM0.8) at 10,000 rpm to obtain a dispersion of long and fine aramid single fibers.
  • a homomixer Principal Corporation, MARKII2.5 type
  • CLM0.8 clear mixer
  • the obtained long fine aramid single fiber dispersion was suction filtered through a membrane filter having a hole diameter of 0.2 ⁇ m and dried in an oven at 105° C., and the maximum fiber diameter, minimum fiber diameter, maximum fiber length, minimum fiber length, soluble content, crystallinity and glass transition point of the long fine aramid single fibers were measured (see FIGS. 1 to 3 and Table 1).
  • the obtained dispersion of long and fine aramid single fibers was centrifuged at 16,000 G, the dimethyl sulfoxide was removed by decantation, and the precipitate was collected. The above precipitate was mixed with N,N'-dimethylacetamide, centrifuged again at 16,000 G, and decanted to recover the precipitate.
  • Example 2 Preparation of a composite material containing 10% by mass of long fine aramid single fibers
  • a solvent 10 g of dimethylacetamide and 10 g of acetone were mixed, and 51.09 g of base material EPICLON850, 28.27 g of hardener TD-2131, and 0.794 g of hardener 2P4MHZ-pw were added and stirred until the appearance became uniform, and 80.1 g of the paste containing the long fine aramid single fibers produced in Example 1 was further added.
  • the resulting composition was stirred and degassed in a share mixer (SK-300SII, manufactured by KAKUHUNTER) and cast onto a PET film. The cast PET film was heated on a hot plate at 100° C.
  • Example 3 Preparation of a composite material containing 30% by mass of long fine aramid single fibers
  • 10 g of dimethylacetamide and 10 g of acetone were mixed, and 51.09 g of base material EPICLON850, 28.27 g of hardener TD-2131, and 0.794 g of hardener 2P4MHZ-pw were added and stirred until the appearance became uniform, and 240.3 g of the paste containing the long fine aramid single fibers produced in Example 1 was further added.
  • the resulting composition was stirred and degassed in a share mixer (SK-300SII, manufactured by KAKUHUNTER) and cast onto a PET film. The cast PET film was heated on a hot plate at 100° C.
  • Comparative Example 1 Preparation of amorphous aramid nanofibers 3 g of potassium hydroxide and 4 g of water were stirred, and then added to 2 g of raw material aramid fibers dried in an oven at 105° C. for 24 hours and 198 g of dimethyl sulfoxide, heated at 70° C., stirred for 60 minutes, and further mixed with 100 g of dimethyl sulfoxide to prepare an aramid fiber dispersion. The obtained aramid fiber dispersion was poured into a vessel containing 2 L of deionized water with stirring.
  • the above deionized water was neutralized with sulfuric acid until the pH of the water reached 7 ⁇ 0.1 as measured by a pH meter (LAQUAtwin manufactured by Horiba, Ltd.), centrifuged at 16,000 G, the supernatant was removed by decantation, 200 g of deionized water was added, and the mixture was centrifuged again at 16,000 G. The supernatant was removed by decantation, and 200 g of deionized water was added to obtain an amorphous aramid nanofiber dispersion. The obtained amorphous aramid nanofiber dispersion was dried, and the maximum fiber diameter, minimum fiber diameter, maximum fiber length, minimum fiber length, soluble content, and glass transition point were measured.
  • the crystallinity of the amorphous aramid nanofiber was set to 0 (see Table 1). Meanwhile, 220 g of the obtained amorphous aramid nanofiber dispersion was dried in an oven at 105° C., and 198 g of dimethylacetamide was added thereto and mixed until uniformly dispersed. The mixture was centrifuged at 16,000 G and decanted to obtain a paste of amorphous aramid nanofiber. The solid content of the resulting paste was 10% by mass.
  • Raw material aramid fiber TAK. inc.
  • Comparative Example 2 Preparation of a composite material containing 10% by mass of amorphous aramid nanofibers A composite material was produced in the same manner as in Example 2, except that the paste of amorphous aramid nanofiber obtained in Comparative Example 1 was used.
  • Comparative Example 3 Preparation of a composite material containing 30% by mass of amorphous aramid nanofibers A composite material was produced in the same manner as in Example 3, except that the paste of amorphous aramid nanofiber obtained in Comparative Example 1 was used.
  • the maximum fiber diameter, minimum fiber diameter, maximum fiber length, minimum fiber length, soluble content, crystallinity, and glass transition temperature (Tg) of the long fine aramid single fiber of Example 1 and the amorphous aramid nanofiber of Comparative Example 1 are shown in Table 1 below.
  • Example 2 The dielectric strength of the composite materials of Example 2 and Comparative Example 2, as well as the glass transition point and soluble content of Example 3 and Comparative Example 3, are shown in Table 2 below.
  • the long fine aramid single fiber obtained in Example 1 had a maximum fiber diameter of 1960 nm, a minimum fiber diameter of 300 nm, a maximum fiber length of 360 um, a minimum fiber length of 70 ⁇ m, and a degree of crystallinity of 80%, and it was confirmed by SEM observation that it was a single fiber without branching ( Figures 1 to 3).
  • the amorphous aramid nanofiber obtained in Comparative Example 1 had a maximum fiber diameter of 200 nm, a minimum fiber diameter of 10 nm, a maximum fiber length of 10 ⁇ m, and a minimum fiber length of 0.1 um.
  • Examples 2 and 3 which are composite materials containing long fine aramid single fibers and a matrix resin, was high at 27.5 kV/mm, the glass transition point rose to 130°C or higher, and the soluble content was 0 mass%.

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Abstract

La présente invention concerne une fibre unique d'aramide longue-fine ayant un diamètre de fibre maximal inférieur à 2000 nm et une longueur de fibre minimale supérieure à 10 µm, le degré x de cristallinité déterminé par l'expression x=(1-∆Qx/∆Q0)×100 (%) (dans l'expression, ∆Qx étant une quantité de changement de capacité thermique avant et après le point de transition vitreuse de la fibre unique d'aramide longue-fine, et ∆Q0 étant une quantité de changement de capacité thermique avant et après le point de transition vitreuse d'un aramide amorphe) étant d'au moins 60%. La présente invention peut fournir une fibre unique d'aramide qui est très fine et longue et a un degré élevé de cristallinité.
PCT/JP2024/023019 2023-07-04 2024-06-25 Fibre unique d'aramide longue-fine, son procédé de fabrication, et matériau composite et feuille contenant une fibre unique d'aramide longue-fine Pending WO2025009443A1 (fr)

Priority Applications (2)

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KR1020257041390A KR20260035817A (ko) 2023-07-04 2024-06-25 장 미세 아라미드 단섬유 및 그 제조 방법, 그리고 장 미세 아라미드 단섬유를 포함하는 복합 재료 및 시트
CN202480041849.5A CN121420100A (zh) 2023-07-04 2024-06-25 长微细芳酰胺单纤维及其制造方法、以及包含长微细芳酰胺单纤维的复合材料与片材

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JP2023110047A JP2025008135A (ja) 2023-07-04 2023-07-04 長微細アラミド単繊維及びその製造方法並びに長微細アラミド単繊維を含む複合材料及びシート
JP2023-110047 2023-07-04

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200779A (ja) * 2004-01-14 2005-07-28 Teijin Ltd パラ型芳香族ポリアミド系繊維、繊維構造体およびその製造方法
JP2009007702A (ja) * 2007-06-28 2009-01-15 Gun Ei Chem Ind Co Ltd 結晶性高分子超細繊維の製造法
JP2021118055A (ja) * 2020-01-23 2021-08-10 ニッポン高度紙工業株式会社 リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
JP2023002089A (ja) * 2021-06-22 2023-01-10 帝人株式会社 セパレーターおよびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200779A (ja) * 2004-01-14 2005-07-28 Teijin Ltd パラ型芳香族ポリアミド系繊維、繊維構造体およびその製造方法
JP2009007702A (ja) * 2007-06-28 2009-01-15 Gun Ei Chem Ind Co Ltd 結晶性高分子超細繊維の製造法
JP2021118055A (ja) * 2020-01-23 2021-08-10 ニッポン高度紙工業株式会社 リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
JP2023002089A (ja) * 2021-06-22 2023-01-10 帝人株式会社 セパレーターおよびその製造方法

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